Methods for producing emulsifiers for oil-based drilling fluids

ABSTRACT

Methods for making emulsifiers, emulsified drilling fluids, and methods for using the same are provided. In one or more embodiments, the method for making an emulsifier can include mixing a tall oil and a triamide. The triamide can have the chemical formula: 
     
       
         
         
             
             
         
       
     
     where:
         x, y, and z are integers independently selected from 1 to 10,   R 1  is a C 8 -C 20  alkyl, a C 8 -C 20  alkenyl, a C 8 -C 20  dialkenyl, or a C 8 -C 20  alkynyl,   R 2  is H or       

     
       
         
         
             
             
         
       
     
     independently selected for each [(CH 2 ) x NR 2 (CH 2 ) y ] unit, where R 4  is a C 1 -C 3  alkylene or a C 1 -C 3  alkylene alcohol, and where at least one R 2  is 
     
       
         
         
             
             
         
       
     
     and
         R 3  is a C 8 -C 20  alkyl, a C 8 -C 20  alkenyl, a C 8 -C 20  dialkenyl, or a C 8 -C 20  alkynyl.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a continuation of co-pending U.S. patent applicationSer. No. 14/461,460, filed on Aug. 18, 2014, which claims priority toU.S. Provisional Patent Application No. 61/867,328, filed Aug. 19, 2013,which are both incorporated by reference herein.

BACKGROUND Field

Embodiments described generally relate to methods for making emulsifiersthat can include one or more tall oils and one or more triamides,emulsified drilling fluids, and methods for using same.

Description of the Related Art

The oil and gas industry has used drilling fluids or “drilling muds” fora number of years to tap subterranean deposits of natural resources. Asthe total reserves of oil diminish, it has become necessary to drill inareas that were previously inaccessible due to technological or economicdifficulties. This has led to the widespread use of oil-based drillingfluids or invert emulsion drilling fluids, which offer greater thermaland chemical stability than water-based fluids, allowing for drilling atextended depths and in other demanding services, such as those involvingexposure to high electrolyte concentrations and soluble gases. Forexample, invert emulsion drilling fluids have been used successfully indrilling hot (e.g., greater than 150° C.) formations as well as thosecontaining hydrogen sulfide. Also, to maximize recovery from eachplatform in offshore drilling, invert emulsion drilling fluids arefavored due to their effectiveness for drilling deviated wells (e.g.,angled wells). In particular, the high lubricity of invert emulsiondrilling fluids is necessary because of the increased torque exerted onthe drill string in deviated drilling.

Invert emulsion drilling fluids are typically formed by blending ahydrocarbon oil with water or brine under high shear conditions and inthe presence of a suitable emulsifier. The emulsifier is required notonly to form a stable dispersion of water droplets in the oil phase, butalso to maintain any solids such as weighting material additives (e.g.,barites) or drill cuttings in an oil-wet state. With space at some wellsites limited, such as on offshore platforms, and with increasing costsof transport of materials to a well site, there is industry wideinterest particularly in drilling fluid compositions that can beformulated and maintained (e.g., stored) with minimal or fewerquantities of solvent and other additives, compared to prior artcompositions.

There is a need, therefore, for improved emulsifiers for use in invertemulsions that can be used, for example, in oil well drilling.

SUMMARY

Methods for making emulsifiers, emulsified drilling fluids, and methodsfor using the same are provided. In one or more embodiments, the methodfor making an emulsifier can include mixing a tall oil and a triamide.The triamide can have the general chemical formula, Formula (I):

where:

-   -   x, y, and z are integers independently selected from 1 to 10,    -   R¹ is a C₈-C₂₀ alkyl, a C₈-C₂₀ alkenyl, a C₈-C₂₀ dialkenyl, or a        C₈-C₂₀ alkynyl,    -   R² is H or

-   -   independently selected for each [CH₂)_(x)NR²(CH₂)_(y)] unit,        where R⁴ is a C₁-C₃ alkylene or a C₁-C₃ alkylene alcohol, and        where at least one R² is

-   -   and    -   R³ is a C₈-C₂₀ alkyl, a C₈-C₂₀ alkenyl, a C₈-C₂₀ dialkenyl, or a        C₈-C₂₀ alkynyl.

In some embodiments, the method for making an emulsifier can includemixing a triamide and a tall oil. The triamide can be prepared byreacting a diamidoamine with a saturated dicarboxylic acid, a saturatedacid anhydride, or a mixture thereof. The method can also include spraydrying the emulsifier to provide a spray dried emulsifier.

The method for making a drilling fluid can include mixing an oil phase,an aqueous phase, and a spray dried emulsifier to produce a drillingfluid. The spray dried emulsifier can include a mixture of a tall oiland a triamide, where the triamide can have Formula (I).

DETAILED DESCRIPTION

Methods for making emulsifiers, emulsified drilling fluids, and methodsfor using the same are provided. In one or more embodiments, theemulsifier can be made by mixing, blending, or otherwise combining oneor more tall oils and one or more triamides. The one or more triamidescan be represented by the general chemical formula, Formula (I):

where:

-   -   x, y, and z are integers independently selected from 1 to 10,    -   R² is a C₈-C₂₀ alkyl, a C₈-C₂₀ alkenyl, a C₈-C₂₀ dialkenyl, or a        C₈-C₂₀ alkynyl,    -   R² is H or

-   -   independently selected for each [CH₂)_(x)NR²(CH₂)_(y)] unit,        where R⁴ is a C₁-C₃ alkylene or a C₁-C₃ alkylene alcohol, and        where at least one R² is

-   -   and    -   R³ is a C₈-C₂₀ alkyl, a C₈-C₂₀ alkenyl, a C₈-C₂₀ dialkenyl, or a        C₈-C₂₀ alkynyl.

The C₁-C₃ alkylene for R⁴ can include, but is not limited to, amethylene or methanediyl group (—CH₂—), an ethylene or ethanediyl group(—CH₂CH₂—), and a propylene or propanediyl group (—CH₂CH₂CH₂—), whichprovides a saturated alkane moiety in the triamide. The C₁-C₃ alkylenealcohol for R⁴ can include, but is not limited to, a methylene ormethanediyl alcohol group (—C(OH)H—), an ethylene or ethanediyl alcoholgroup (—CH₂C(OH)H—), and a propylene or propanediyl alcohol group(—CH₂C(OH)HCH₂— or —CH₂CH₂C(OH)H—), which provides a saturated alkanealcohol moiety in the triamide.

In some embodiments, the emulsifier can be used for oil-based drillingfluids. It has been surprisingly and unexpectedly discovered that whenR⁴ is a C₁-C₃ alkylene or a C₁-C₃ alkylene alcohol, e.g., a saturatedcarbon chain, the oil-based drilling fluids can exhibit one or more ofthe following properties: flatter low end rheology, lower high endrheology, higher electrical stability, lower plastic viscosity, lowergel strengths, and lower fluid loss to the subterranean formation, ascompared to the same emulsifier, but having an unsaturated R⁴, e.g., anR⁴ having at least one carbon-carbon double bond. For example, theemulsifier having R⁴ as a C₁-C₃ alkylene or a C₁-C₃ alkylene alcohol canimprove the low end rheology, the high end rheology, the electricalstability, the gel strengths, plastic viscosity, fluid break-through,and/or the fluid loss by about 0.2%, about 0.5%, about 1%, about 2%,about 3%, about 4%, about 5%, or about 10%, or more as compared to thesame emulsifier but having an unsaturated R⁴, such as when R⁴ isalkenylene (e.g., —(C_(n)H_(2n-2))—, where n is 1, 2, or 3).

The one or more tall oils and the one or more triamides of theemulsifier can be combined with one another in any ratio. For example,the weight ratio of the triamide to the tall oil can be about 99:1,about 90:10, about 80:20, about 70:30, about 60:40, or about 50:50 toabout 40:60, about 30:70, about 20:80, about 10:90, or about 1:99. Inanother example, the weight ratio of the triamide to tall oil can beabout 0.5:1, about 1:1, about 2:3, about 3:7, or about 1:4. In anotherexample, the weight ratio of the triamide to tall oil can be about 0.1:1to about 3:1, about 0.2:1 to about 2.8:1, about 0.3:1 to about 2.5:1,about 0.4:1 to about 2.2:1, about 0.5:1 to about 2:1, about 0.3:1 toabout 2:1, about 1:1 to about 3:1, about 0.4:1 to about 1:1, about 0.4:1to about 0.7:1, or about 0.3:1 to about 1:1.

In some embodiments, the emulsifier can have an acid value of about 100mg of KOH, about 125 mg of KOH, or about 150 mg of KOH to about 250 mgof KOH, about 175 mg of KOH, about 200 mg of KOH, per gram ofemulsifier. For example, the emulsifier can have an acid value of about100 mg of KOH to about 150 mg of KOH, about 125 mg of KOH to about 175mg of KOH, about 170 mg of KOH to about 200 mg of KOH, about 170 mg ofKOH to about 225 mg of KOH, about 165 mg of KOH to about 230 mg of KOH,about 180 mg of KOH to about 220 mg of KOH, about 200 mg of KOH to about250 mg of KOH, about 225 mg of KOH to about 250 mg of KOH, or about 250mg of KOH to about 300 mg of KOH, per gram of emulsifier. In anotherexample, the emulsifier can have an acid value of at least 100 mg ofKOH, at least 110 mg of KOH, at least 120 mg of KOH, at least 130 mgKOH, at least 150 mg KOH, or at least 175 mg KOH. In another example,the emulsifier can have an acid value of less than 220 mg KOH, less than170 mg KOH, or less than 150 mg KOH.

As used herein, the term “acid value” refers to the mass of potassiumhydroxide (KOH) in milligrams that is required to neutralize one gram ofa reaction mixture or a composition. For example, the acid value of theemulsifier refers to the amount of KOH in milligrams required toneutralize one gram of the emulsifier. The acid value can be used as ameasure of the amount of carboxylic acid groups in a reaction mixture ora composition. In a typical procedure, a known amount of the compositionis dissolved in organic solvent and titrated with a solution ofpotassium hydroxide of known concentration. The acid value can bedetermined by using a potassium hydride solution that containsphenolphthalein as a color indicator or using potentiometric analysis.Standard methods used for determining acid value include ASTM D 465-05and AOCS Te 1a-64.

The rheology, electrical stability, gel strengths, plastic viscosity,yield point, high temperature/high pressure, fluid break-through, andfluid loss can be tested according to the API Recommended PracticeStandard 13B-2, Third Edition, February 1998. The drilling fluid canhave a rheology of about 3, about 5, or about 7 to about 15, about 17,or about 20, after hot roll at 3 rotations per minute (rpm) at 150° F.For example, the drilling fluid can have a rheology of about 4 to about7, about 5 to about 10, about 6 to about 17, about 8 to about 15, orabout 8 to about 28, after hot roll at 3 rpm at 150° F. The drillingfluid can have a rheology of about 3, about 5, or about 7 to about 15,about 17, about 23, about 27, or about 30, after hot roll at 6 rpm at150° F. For example, the drilling fluid can have a rheology of about 4to about 7, about 5 to about 10, about 6 to about 17, about 8 to about15, or about 6 to about 28, after hot roll at 6 rpm at 150° F. Thedrilling fluid can have a rheology of about 45, about 50, or about 55 toabout 70, about 75, about 85, after hot roll at 600 rpm at 150° F. Forexample, the drilling fluid can have a rheology of about 40 to about 70,about 50 to about 67, about 50 to about 70, or about 55 to about 85,after hot roll at 600 rpm at 150° F.

The drilling fluid containing the emulsifier can have a ten second gelstrength of about 3 lb/100 ft², about 5 lb/100 ft², or about 7 lb/100ft² to about 15 lb/100 ft², about 17 lb/100 ft², about 30 lb/100 ft²,after hot roll at 150° F. For example, the drilling fluid can have a tensecond gel strength of about 4 lb/100 ft² to about 7 lb/100 ft², about 5lb/100 ft² to about 10 lb/100 ft², about 6 lb/100 ft² to about 17 lb/100ft², about 8 lb/100 ft² to about 15 lb/100 ft², or about 14 lb/100 ft²toabout 28 lb/100 ft², after hot roll at 150° F.

The drilling fluid containing the emulsifier can have a ten minute gelstrength of about 3 lb/100 ft², about 5 lb/100 ft², or about 7 lb/100ft² to about 15 lb/100 ft², about 17 lb/100 ft², about 30 lb/100 ft²,after hot roll at 150° F. For example, the drilling fluid can have a tenminute gel strength of about 4 lb/100 ft² to about 7 lb/100 ft², about 5lb/100 ft² to about 10 lb/100 ft², about 6 lb/100 ft² to about 17 lb/100ft², about 8 lb/100 ft² to about 15 lb/100 ft², or about 14 lb/100 ft²to about 28 lb/100 ft², after hot roll at 150° F.

The drilling fluid containing the emulsifier can have a plasticviscosity of about 15 cP, about 17 cP, or about 19 cP to about 25 cP,about 27 cP, about 30 cP, after hot roll at 150° F. For example, thedrilling fluid can have a plastic viscosity of about 15 cP to about 17cP, about 5 cP to about 10 cP, about 6 cP to about 17 cP, about 8 cP toabout 15 cP, or about 14 cP to about 28 cP, after hot roll at 150° F.

The drilling fluid containing the emulsifier can have a yield point ofabout 3 lb/100 ft², about 5 lb/100 ft², or about 7 lb/100 ft² to about15 lb/100 ft², about 17 lb/100 ft², about 30 lb/100 ft², after hot rollat 150° F. For example, the drilling fluid can have a yield point ofabout 4 lb/100 ft² to about 7 lb/100 ft², about 5 lb/100 ft² to about 10lb/100 ft², about 6 lb/100 ft² to about 17 lb/100 ft², about 8 lb/100ft² to about 15 lb/100 ft², or about 8 lb/100 ft² to about 28 lb/100ft², after hot roll at 150° F.

The drilling fluid containing the emulsifier can have higher electricalstability. The drilling fluid containing the emulsifier can have anelectrical stability of about 600 V, about 700 V, or about 725 V toabout 800 V, about 1,000 V, or about 1,200 V, at 150° F. For example,the drilling fluid containing the emulsifier can have an electricalstability of about 600 V to about 650 V, about 650 V to about 700 V,about 675 V to about 750 V, about 700 V to about 760 V, about 725 V toabout 850 V, about 825 V to about 950 V, about 925 V to about 1,100 V,or about 1,000 V to about 1,200 V, at 150° F.

The drilling fluid containing the emulsifier can have hightemperature/high pressure fluid loss of about 5 mL, about 6 mL, or about7 mL to about 10 mL, about 12 mL, about 14 mL, after hot roll at 150° F.For example, the drilling fluid can have a fluid loss of about 4 mL toabout 7 mL, about 5 mL to about 10 mL, about 6 mL to about 11 mL, orabout 8 mL to about 14 mL, after hot roll at 150° F.

The drilling fluid containing the emulsifier can exhibit minimal waterbreak-through under high temperature/high pressure testing conditions.The drilling fluid containing the emulsifier can have a waterbreak-through value of about 0 mL, about 0.1 mL, or about 0.2 mL toabout 0.5 mL, at high temperature/high pressure testing conditions. Forexample, the drilling fluid containing the emulsifier can have a waterbreak-through value of about 0 mL to about 0.1 mL, about 0.1 mL to about0.2 mL, about 0.2 mL to about 0.3 mL, about 0.3 mL to about 0.4 mL, orabout 0.4 mL to about 0.5 mL, at high temperature/high pressure testingconditions.

The compounds of Formula (I) can be made using one or more differentsynthetic routes. One exemplary synthetic route can include sequentialcondensation reactions as shown in Scheme (I) below. More particularly,a polyamine can be reacted with fatty acids to produce an amidoamineproduct. The amidoamine product can be reacted with a succinic anhydrideto produce a triamide. In the specific embodiment depicted in Scheme(I), two molecules of the same kind of fatty acid are reacted withdiethylenetriamine as the polyamine to form a diamidoamine or“intermediate product.” In a subsequent condensation reaction, thediamidoamine is reacted with succinic anhydride as the saturateddicarboxylic acid to produce a triamide. Exemplary Scheme (I) is asfollows:

It can be seen that the triamide depicted in Scheme (I) has themolecular structure of Formula (I), where R¹ and R⁴ are the same.

The reaction conditions, e.g., heating, can be controlled to favor themore thermodynamically stable amide product. Any of the amine functionalgroups on the polyamine can undergo a condensation reaction with thecarboxylic acid group of the fatty acid; however, the primary amines canbe more kinetically favored than the secondary amines on the polyamine.By controlling the reaction conditions, such as the concentration of thereactants, the reaction of one fatty acid molecule for every primaryamine on the polyamine can be favored. A thermodynamically andkinetically favored diamidoamine has been depicted in Reaction 1 ofScheme (I).

The diamidoamine can then be reacted with a saturated dicarboxylic acidand/or a saturated acid anhydride. Reaction 2 of Scheme (I) depicts acondensation reaction between the diamidoamine and succinic anhydride.At least one of the acyl moieties on the succinic anhydride can reactwith at least one of the secondary amine functional groups on thediamidoamine (for diethylenetriamine only one secondary amine ispresent) to form a third amide group. The second acyl moiety on theanhydride can react with a second diamidoamine in the reaction mixture,e.g., two diamidoamine molecules can react with one anhydride compound.By controlling the reaction conditions, however, such as theconcentrations of the reactants, the reaction between one diamidoaminemolecule and one dicarboxylic acid or acid anhydride molecule can befavored. Also, if the reaction is performed with an acid anhydridecompound instead of a dicarboxylic acid compound, a lower temperaturecan be used, which leads to less cross-linking between diamidoamines. Inone or more examples, the reaction product can be triamide, asillustrated in Reaction 2 of Scheme (I).

In one or more examples, after a single condensation reaction of thefatty acid and the polyamine, a self-cyclization reaction can produce animidazoline (e.g., a 1-aminoalkyl-2-alkyl-2-imidazoline). For clarity,Reaction 3 has been included to show an exemplary imidazoline productwhen the reactant polyamine is diethylenetriamine.

The reaction mixture for the diamidoamine and, if the subsequentreaction is performed in a single pot, the reaction mixture for thetriamide can also include the imidazoline product. The primary amine ofthe imidazoline product can also react with the saturated dicarboxylicacid and/or saturated acid anhydride. Because the imidazoline product isless effective as an emulsifier, the reaction conditions, such asreaction temperature, can be chosen to limit the imidazoline reactionproduct. Exemplary reaction conditions for limiting the imidazolinereaction product can include those discussed and described in U.S. Pat.No. 3,758,493.

One or more fatty acids, one or more polyamines, and one or more liquidmedia can be mixed to from a diamidoamine reaction mixture. The molarratio of the carboxylic acid group on the fatty acid to the primaryamine groups on the polyamine can be used to favor a reaction betweenone fatty acid molecule for every primary amine group on the polyamine.For example, e molar ratio of the carboxylic acid group to the primaryamine group can be about 0.5:1 to about 1.1:1. In another example, themolar ratio of the carboxylic acid group to the primary amine group canbe about 0.5:1 to about 0.7:1, about 0.6:1 to about 0.8:1, about 0.7:1to about 1:1, about 0.9:1 to about 1:1, or about 0.8:1 to about 1.1:1.

The diamidoamine reaction mixture can be heated to a temperature ofabout 130° C., about 140° C., about 145° C. to about 170° C., about 180°C., or about 200° C. For example, the reaction temperature can be about140° C. to about 150° C., about 145° C. to about 155° C., about 155° C.to about 165° C., about 160° C. to about 170° C., about 155° C. to about170° C., about 160° C. to about 190° C., or about 180° C. to about 200°C. The diamidoamine reaction mixture of the fatty acids and thepolyamine can be heated for, or otherwise have a reaction time of, about0.5 hours, about 1 hour, about 2 hours, about 3 hours, about 4 hours,about 5 hours, about 6 hours, about 7 hours, about 8 hours, about 9hours, about 10 hours, about 11 hours, about 12 hours, or greater. Forexample, the fatty acids and the polyamine can be heated or reacted forabout 0.7 hours to about 1.3 hours, about 0.7 hours to about 1.3 hours,about 1 hour to about 3 hours, about 1.5 hours to about 4 hours, about 2hours to about 5 hours, about 3 hours to about 7 hours, about 5 hours toabout 8 hours, about 6 hours to about 10 hours, about 8 hours to about12 hours.

The fatty acids and the polyamine can be reacted until a desired acidvalue is obtained. The diamidoamine reaction mixture can have an acidvalue of about 3 mg of KOH, about 5 mg of KOH, or about 7 mg of KOH toabout 15 mg of KOH, about 20 mg of KOH, or about 25 mg of KOH, per gramof diamidoamine reaction mixture. For example, the diamidoamine reactionmixture can have an acid value of about 3 mg of KOH to about 5 mg ofKOH, about 4 mg of KOH to about 8 mg of KOH, about 7 mg of KOH to about12 mg of KOH, about 9 mg of KOH to about 15 mg of KOH, about 10 mg ofKOH to about 16 mg of KOH, about 14 mg of KOH to about 20 mg of KOH,about 16 mg of KOH to about 25 mg of KOH, per gram of diamidoaminereaction mixture.

The diamidoamine reaction mixture can include a solvent or diluent, alsoreferred to as “liquid medium.” The diamidoamine reaction can also beperformed neat so the diamidoamine reaction mixture can be free ofsolvent or liquid medium. The diamidoamine reaction mixture can have aliquid medium concentration of about 0.1 wt %, about 1 wt %, or about 3wt % to about 10 wt %, about 15 wt %, or about 20 wt %, based on thecombined weight of the fatty acids, the polyamines, and the liquidmedium. In another example, the diamidoamine reaction mixture can have aliquid medium concentration of about 0.1 wt % to about 3 wt %, about 0.1wt % to about 4 wt %, about 1 wt % to about 6 wt %, about 3 wt % toabout 8 wt %, about 7 wt % to about 14 wt %, about 11 wt % to about 17wt %, or about 12 wt % to about 20 wt %, the polyamines, and the liquidmedium. During the reaction, the liquid medium can be distilled orevaporated from the diamidoamine reaction mixture, which can change theconcentration of the liquid medium.

The diamidoamine reaction mixture can have a solids content of about 80wt %, about 85 wt %, or about 90 wt % to about 95 wt %, about 98 wt %,or about 100 wt % (e.g., where the solvent-free system has 100 wt %solids), based on the total weight of the reaction mixture. In anotherexample, the diamidoamine reaction mixture can have a solids content ofabout 80 wt % to about 85 wt %, about 85 wt % to about 90 wt %, about 90wt % to about 95 wt %, about 94 wt % to about 98 wt %, about 96 wt % toabout 99 wt %, or about 96 wt % to about 100 wt %, based on the totalweight of the reaction mixture. As used herein, the solids content, asunderstood by those skilled in the art, can be measured by determiningthe weight loss upon heating a small sample (e.g., about 1 gram to about5 grams) of the reaction mixture, to a suitable temperature, e.g., about125° C., and a time sufficient to remove the liquid therefrom.

Illustrative fatty acids that can be reacted with the polyamine to formthe diamidoamine can include, but are not limited to, the alkanoic andalkenoic fatty acids having from about 6 carbon atoms to about 24 carbonatoms, such as lauric acid, myristic acid, palmitic acid, stearic acid,arachidic acid, behenic acid, oleic acid, linoleic acid, erucic acid, orany combination thereof Mixtures of fatty acids can also be used.Illustrative fatty acids can be provided or used in the form of crudetall oil (CTO), one or more tall oil distillation products, one or morevegetable oils, and any mixture thereof.

In one embodiment, crude tall oil can be made or produced as anacidified byproduct in the kraft or sulfate processing of wood. Crudetall oil, prior to refining, can include a mixture of rosin acids, fattyacids, sterols, high-molecular weight alcohols, and other alkyl chainmaterials. The components of crude tall oil depend on a variety offactors, such as the particular coniferous species of the wood beingprocessed (wood type), the geographical location of the wood source, theage of the wood, the particular season that the wood is harvested, andothers. Thus, depending on the particular source, crude tall oil cancontain about 20 wt % to about 75 wt % of fatty acids (e.g., about 30 wt% to about 60 wt % of fatty acids), about 20 wt % to about 65 wt % ofrosin acids and the balance being the neutral and non-saponifiablecomponents. Crude tall oil can contain at least 10 wt % of neutralmaterials or non-saponifiable components.

Distillation of crude tall oil can be used to recover a mixture of fattyacids in the C₁₆-C₂₀ range. Fatty acids found in tall oils can include,but are not limited to, oleic acid, linoleic acid, stearic acid, andpalmitic acid. Rosin acids found in tall oils, include, but are notlimited to, abietic acid, dehydroabietic acid, isopimaric acid, andpimaric acid. Examples of tall oil distillation products that can beused as the fatty acids or at to make up at least a portion of the fattyacids discussed and described herein can include, but are not limitedto, tall oil fatty acids (TOFA), distilled tall oil (DTO), tall oilpitch, or any mixture thereof.

The distilled tall oil fraction can have a fatty acids and esters offatty acids concentration of about 55 wt %, about 60 wt %, or about 65wt % to about 85 wt %, about 90 wt %, or about 95 wt %. The distilledtall oil fraction can have a rosin acids or rosins concentration ofabout 5 wt %, about 10 wt %, or about 15 wt % to about 30 wt %, about 35wt %, or about 40 wt %. The distilled tall oil fraction can have aneutrals concentration of about 0.1 wt %, about 1 wt %, or about 1.5 wt% to about 2 wt %, about 3.5 wt %, or about 5 wt %. The distilled talloil fraction can have an acid value of about 20, about 25, or about 30to about 40, about 45, or about 50. The distilled tall oil fraction canhave a viscosity (centipoise at 85° C.) of about 10 cP, about 20 cP,about 30 cP, or about 40 cP to about 100 cP, about 120 cP, about 135 cP,or about 150 cP. The distilled tall oil can have a density of about 840g/L, about 860 g/L, or about 880 g/L to about 900 g/L, about 920 g/L, orabout 935 g/L. The distilled tall oil fraction can have a saponificationnumber of about 180, about 185, or about 190 to about 200, about 205, orabout 210. The distilled tall oil fraction can have an iodine value ofabout 115, about 117, or about 120 to about 130, about 135, or about140.

The rosin acids derived from crude tall oil are also an intermediatefraction that can be produced from the distillation of crude tall oil.The tall oil rosin can have a concentration of rosin acids of about 80wt %, about 85 wt %, or about 90 wt % to about 93 wt %, about 95 wt %,or about 99 wt %. The tall oil rosin can have a concentration of abieticacid of about 35 wt %, about 40 wt %, or about 43 wt % to about 50 wt %,about 55 wt %, or about 60 wt %. The tall oil rosin can have aconcentration of dehydroabietic acid of about 10 wt %, about 13 wt %, orabout 15 wt % to about 20 wt %, about 23 wt %, or about 25 wt %. Thetall oil rosin can have a concentration of isopimaric acid of about 10wt % or less, about 8 wt % or less, about 5 wt % or less, or about 3 wt% or less. The tall oil rosin can have a concentration of pimaric acidof about 10 wt % or less, about 8 wt % or less, about 5 wt % or less, orabout 3 wt % or less. The tall oil rosin can have a fatty acidsconcentration of about 0.5 wt %, about 1 wt %, or about 2 wt % to about3 wt %, about 5 wt %, or about 10 wt %. The tall oil rosin can have aconcentration of neutral materials of about 0.5 wt %, about 1 wt %, orabout 2 wt % to about 3 wt %, about 5 wt %, or about 10 wt %. The talloil rosin can have a density of about 960 g/L, about 970 g/L, or about980 g/L to about 1,000 g/L, about 1,010 g/L, or about 1,020 g/L. Thetall oil rosin can have an acid value of about 150, about 160, or about165 to about 170, about 175, or about 180.

Representative tall oil products can include saturated and unsaturatedfatty acids in the C₁₆-C₁₈ range, as well as minor amounts of rosinacids, and can include XTOL® 100, XTOL® 300, and XTOL® 304, XTOL® 520,and LYTOR® 100, all of which are commercially available fromGeorgia-Pacific Chemicals LLC, Atlanta, Ga. XTOL® 100 includes about 1.6wt % of palmitic acid, about 2.5 wt % of stearic acid, about 37.9 wt %of oleic acid, about 26.3 wt % of linoleic acid, about 0.3 wt % oflinolenic acid, about 2.9 wt % of linoleic isomers, about 0.2 wt % ofarachidic acid, about 3.6 wt % eicosatrienoic acid, about 1.4 wt % ofpimaric acid, <0.16 wt % of sandarocopimaric, <0.16 wt % of isopimaricacid, <0.16 wt % of dehydroabietic acid, about 0.2 wt % of abietic acid,with the balance being neutrals and high molecular weight species.LYTOR® 100 includes <0.16 wt % of palmitic acid, <0.16 wt % of stearicacid, about 0.2 wt % of oleic acid, about 0.2 wt % of arachidic acid,about 0.2 wt % eicosatrienoic acid, about 2.2 wt % of pimaric acid,about 0.6 wt % of sandarocopimaric, about 8.5 wt % of palustric acid,about 1.6 wt % of levopimaric acid, about 2.8 wt % of isopimaric acid,about 15.3 wt % of dehydroabietic acid, about 51.4 wt % of abietic acid,about 2.4 wt % of neoabietic acid, with the balance being neutrals andhigh molecular weight species. XTOL® 520 DTO includes about 0.2 wt % ofpalmitic acid, about 3.3 wt % of stearic acid, about 37.9 wt % of oleicacid, about 26.3 wt % of linoleic acid, about 0.3 wt % of linolenicacid, about 2.9 wt % of linoleic isomers, about 0.2 wt % of arachidicacid, about 3.6 wt % eicosatrienoic acid, about 1.4 wt % of pimaricacid, <0.16 wt % wt % of sandarocopimaric, <0.16 wt % of isopimaricacid, <0.16 wt % of dehydroabietic acid, about 0.2 wt % of abietic acid,with the balance being neutrals and high molecular weight species. Suchtall oil products can be used in the reaction with the polyamine or amixture of polyamines. Other fatty acids and mixtures of fatty acids,including oxidized and/or dimerized tall oil, such those discussed belowcan also be employed.

Illustrative vegetable oils that can be used as the fatty acids caninclude, but are not limited to, safflower oil, grapeseed oil, sunfloweroil, walnut oil, soybean oil, cottonseed oil, coconut oil, corn oil,olive oil, palm oil, palm olein, peanut oil, rapeseed oil, canola oil,sesame oil, hazelnut oil, almond oil, beech nut oil, cashew oil,macadamia oil, mongongo nut oil, pecan oil, pine nut oil, pistachio oil,grapefruit seed oil, lemon oil, orange oil, watermelon seed oil, bittergourd oil, buffalo gourd oil, butternut squash seed oil, egusi seed oil,pumpkin seed oil, borage seed oil, blackcurrant seed oil, eveningprimrose oil, açaaí oil, black seed oil, flaxseed oil, carob pod oil,amaranth oil, apricot oil, apple seed oil, argan oil, avocado oil,babassu oil, ben oil, borneo tallow nut oil, cape chestnut, algarobaoil, cocoa butter, cocklebur oil, poppyseed oil, cohune oil, corianderseed oil, date seed oil, dika oil, false flax oil, hemp oil, kapok seedoil, kenaf seed oil, lallemantia oil, mafura oil, manila oil, meadowfoamseed oil, mustard oil, okra seed oil, papaya seed oil, perilla seed oil,persimmon seed oil, pequi oil, pili nut oil, pomegranate seed oil, prunekernel oil, quinoa oil, ramtil oil, rice bran oil, royle oil, shea nutoil, sacha inchi oil, sapote oil, seje oil, taramira oil, tea seed oil,thistle oil, tigernut oil, tobacco seed oil, tomato seed oil, wheat germoil, castor oil, colza oil, flax oil, radish oil, salicornia oil, tungoil, honge oil, jatropha oil, jojoba oil, nahor oil, paradise oil,petroleum nut oil, dammar oil, linseed oil, stillingia oil, vernoniaoil, amur cork tree fruit oil, artichoke oil, balanos oil, bladderpodoil, brucea javanica oil, burdock oil, candlenut oil, carrot seed oil,chaulmoogra oil, crambe oil, croton oil, cuphea oil, honesty oil, mangooil, neem oil, oojon oil, rose hip seed oil, rubber seed oil, seabuckthorn oil, sea rocket seed oil, snowball seed oil, tall oil, tamanuoil, tonka bean oil, ucuhuba seed oil, or any mixture thereof.

If the fatty acid includes two or more fatty acids, each fatty acid canbe present in the same concentration or different concentrations withrespect to one another. For example, a first fatty acid can be presentin a weight ratio of about 99:1, about 90:10, about 80:20, about 70:30,about 60:40, about 50:50, about 40:60, about 30:70, about 20:80, about10:90, or about 1:99 with respect to another or “second” fatty acidcontained therein. Similarly, if three or more fatty acids are mixed,the three or more fatty acids can be present in any ratio.

The polyamine reacted with the one or more fatty acids to produce thediamidoamine can include, but is not limited to, one or more compoundshaving the general chemical formal, Formula (II):

H₂N[(CH₂)_(x)NH]_(y)H   (II)

where x and y can be integers independently selected from 1 to 10.Representative polyamines include the polyethylene polyamines, when x is2. Of this class of polyalkylene polyamines, specific examples caninclude, dimethylenetriamine (x=1, y=2), diethylenetriamine (x=2, y=2),triethylenetetramine (x=2, y=3), tripropylenetetramine (x=3, y=3)tetraethylenepentamine (x=2, y=4), and pentaethylenehexamine (x=2, y=5).

The polyamine can be or include a mixture of two or more polyamines. Ifthe polyamines include two or more polyamines, each polyamine can bepresent in the same concentration or different concentrations withrespect to one another. For example, a first polyamines can be presentin a weight ratio of about 99:1, about 90:10, about 80:20, about 70:30,about 60:40, about 50:50, about 40:60, about 30:70, about 20:80, about10:90, or about 1:99 with respect to another or “second” polyaminecontained therein. Similarly, if three or more polyamines are mixed, thethree or more polyamines can be present in any ratio.

The liquid medium, if present, can be or include water. The water can beadded or generated during the condensation reactions or both. The liquidmedium can also be or include one or more polar aprotic solvents, one ormore polar protic solvents, or any combination thereof. Illustrativepolar aprotic solvents can include, but are not limited to,tetrahydrofuran (“THF”), dimethyl sulfoxide (“DMSO”),N-methylpyrrolidone (“NMP”), dimethyl acetamide, acetone, or anycombination thereof. Illustrative polar protic solvents can include, butare not limited to, methanol, ethanol, propanol, butanol, or anycombination thereof.

One or more diamidoamines, one or more liquid media, and the saturateddicarboxylic acid and/or the saturated acid anhydride can be mixed toform a triamide reaction mixture. The diamidoamine, the liquid media,and the saturated dicarboxylic acid and/or saturated acid anhydride canbe combined with one another in any order or sequence. The diamidoaminecan be isolated from the diamidoamine reaction mixture and then mixedwith the liquid medium and the saturated dicarboxylic acid and/or thesaturated acid anhydride to make the triamide reaction mixture. Or, theliquid medium and the saturated dicarboxylic acid and/or the saturatedacid anhydride can be mixed with the diamidoamine reaction mixture tomake the triamide reaction for a one pot synthesis.

The molar ratio of the carboxylic acid groups on the saturateddicarboxylic acid to the secondary amine groups on the diamidoamine canbe used to favor the reaction product between one saturated dicarboxylicacid molecule and one diamidoamine molecule. For example, the molarratio of carboxylic acid groups to secondary amine groups can be about0.4:1, about 0.5:1, or about 0.7:1 to about 0.9:1, about, 1.0:1, orabout 1.2:1. In another example, the molar ratio of the carboxylic acidgroups to secondary amine groups can be about 0.4:1 to about 0.6:1,about 0.5:1 to about 0.7:1, about 0.7:1 to about 0.9:1, about 0.8:1 toabout 1.1:1, about 0.9:1 to about 1:1, about 0.9:1 to about 1.1:1, orabout 0.9:1 to about 1.2:1.

The molar ratio of the anhydride group on the saturated acid anhydrideto the secondary amine groups on the diamidoamine can be used to favorthe reaction product between one saturated acid anhydride molecule andone diamidoamine molecule. For example, the molar ratio of the anhydridegroup to the secondary amine groups can be about 0.2:1, about 0.4:1, orabout 0.6:1 to about 0.8:1, about 0.9:1, or about 1:1. In anotherexample, the molar ratio of the anhydride group to the secondary aminegroups can be about 0.2:1 to about 1:1, about 0.4:1 to about 0.9:1,about 0.75:1 to about 0.85:1, or about 0.78:1 to about 0.82:1.

The reaction between the diamidoamine and the saturated dicarboxylicacid or the saturated anhydride can be at a temperature of about 25° C.,about 40° C., or about 60° C. to about 130° C. about 150° C. or about175° C. For example, the reaction temperature can be about 30° C. toabout 60° C., about 55° C. to about 85° C., about 60° C. to about 80°C., about 70° C. to about 90° C., about 70° C. to about 80° C., about73° C. to about 95° C., about 92° C. to about 130° C., about 120° C. toabout 160° C., and about 160° C. to about 200° C. Relative to the use ofthe saturated acid anhydride, the use of the saturated dicarboxylic acidto react the terminal amine groups of the fatty acid amine condensate toterminal carboxylic acid groups often requires higher reactiontemperatures.

The reaction time for the reaction between the diamidoamine and thesaturated dicarboxylic acid or the saturated anhydride can be about 0.2hours, about 0.4, or about 0.5 to about 1 hour, about 1.5 hours or about2 hours. For example, the reaction time can be about 0.2 hours to about0.6 hours, about 0.5 hours to about 1 hour, about 0.6 hours to about 0.8hours, about 0.7 hours to about 1 hour, about 1 hour to about 1.5 hours,about 1 hour to about 1.2 hours, or about 1 hour to about 2 hours.Relative to the use of a saturated acid anhydride, the use of asaturated dicarboxylic acid to convert the secondary amine groups to theamide groups often requires longer reaction times.

The diamidoamine and the saturated dicarboxylic acid or the saturatedanhydride can be reacted until a desired acid value is obtained. Theacid value of the triamide reaction mixture can be about 20 mg of KOH,about 30 mg of KOH, or about 40 mg of KOH to about 80 mg of KOH, about90 mg of KOH, or about 100 mg of KOH, per gram of triamide reactionmixture. For example, the triamide reaction mixture can have an acidvalue of about 25 mg of KOH to about 35 mg of KOH, about 30 mg of KOH toabout 50 mg of KOH, about 50 mg of KOH to about 70 mg of KOH, about 55mg of KOH to about 65 mg of KOH, about 60 mg of KOH to about 90 mg ofKOH, about 80 mg of KOH to about 100 mg of KOH, per gram of triamidereaction mixture. The acid value can be used as a measure of the amountof carboxylic acid groups in the triamide reaction mixture.

The triamide reaction mixture can include a solvent or diluent or“liquid medium.” Suitable liquid mediums can be or include those liquidmediums discussed and described above with reference to the diamidoaminereaction mixture. The triamide reaction can also be performed neat sothe triamide reaction mixture can be free of solvent or liquid medium.The triamide reaction mixture can have a liquid medium concentration ofabout 0 wt %, about 1 wt %, or about 3 wt % to about 10 wt %, about 15wt %, or about 20 wt %, based on the combined weight of thediamidoamine, the liquid medium, and the saturated dicarboxylic acidand/or the saturated acid anhydride. In another example, thediamidoamine reaction mixture can have a liquid medium concentration ofabout 0 wt % to about 3 wt %, about 0.1 wt % to about 4 wt %, about 1 wt% to about 6 wt %, about 3 wt % to about 8 wt %, about 7 wt % to about14 wt %, about 11 wt % to about 17 wt %, or about 12 wt % to about 20 wt%, based on the combined weight of the diamidoamine, the liquid medium,and the saturated dicarboxylic acid and/or the saturated acid anhydride.During the reaction, the liquid medium can be distilled, evaporated, orotherwise separated from the triamide reaction mixture, which can changethe concentration of the liquid medium.

The triamide reaction mixture can have a viscosity of about 55 cP, about100 cP, or about 150 cP to about 2,000 cP, about 3,000 cP, or about5,000 cP, at 90° C. For example, the viscosity of the triamide reactionmixture can have a viscosity of about 65 cP to about 105 cP, about 100cP to about 500 cP, about 400 cP to about 1,000 cP, about 900 cP toabout 1,200 cP, about 1,000 cP to about 1,500 cP, about 1,300 cP toabout 1,600 cP, about 1,500 cP to about 2,000 cP, about 1,800 cP toabout 2,600 cP, about 2,000 cP to about 3,000, about 2,500 cP to about4,000, about 3,000 cP to about 5,000, at 90° C. The viscosity can beused to characterize the reaction product. The viscosity can bedetermined using a Brookfield viscometer. The viscometer measures thetorque required to rotate a spindle at constant speed in a solution of adiamidoamine reaction mixture at 25° C. Standard test methods used formeasuring Brookfield viscosity are ASTM D 803-03 and AOCS Ja 10-87 (93).

The triamide reaction mixture can have a solids content of about 80 wt%, about 85 wt %, or about 90 wt % to about 95 wt %, about 98 wt %, orabout 100 wt % (e.g., where the solvent- free system has 100 wt %solids), based on the total weight of the triamide reaction mixture. Inanother example, the diamidoamine reaction mixture can have a solidscontent of about 80 wt % to about 85 wt %, about 85 wt % to about 90 wt%, about 90 wt % to about 95 wt %, about 94 wt % to about 98 wt %, about96 wt % to about 99 wt %, or about 96 wt % to about 100 wt %, based onthe total weight of the triamide reaction mixture. During the reaction,water from the condensation between the diamidoamine and the saturateddicarboxylic acid or the saturated acid anhydride can be distilled fromthe triamide reaction mixture, which can change the solids content.

Representative saturated dicarboxylic acids can include, but are notlimited to, succinic acid, adipic acid, malic acid, and glutaric acidand the like. Representative saturated acid anhydrides can include, butare not limited to, succinic anhydride, adipic anhydride, and glutaricanhydride.

The triamide can be at least partially isolated from triamide reactionmixture or the triamide reaction mixture can be mixed with the tall oilwithout further processing. The triamide and the tall oil can becombined with one another in any order or sequence.

Illustrative tall oils can include, but are not limited to, crude talloil, distilled tall oil, tall oil bottoms, a dimerized tall oil, aDiels-Alder reaction product and/or an ene reaction product of tall oilwith an one or more α,β unsaturated carboxylic acids or acid anhydrides,a Diels-Alder reaction product and/or an ene reaction product of talloil with an one or more α,β unsaturated carboxylic acids or acidanhydrides that has also been dimerized, or any mixture thereof.

Representative tall oil distillate components include tall oil fattyacids, tall oil rosin acids, and mixtures of these fractions. Asmentioned above, the refinement (e.g., fractionation) of tall oil can,for example, provide C₁₆-C₁₈ saturated and unsaturated fatty acids aswell as fatty acid/rosin acid mixtures. Mixtures of tall oil distillatefractions can also be employed as the tall oil distillate component.Fatty acid and rosin acid mixtures in any desired ratio can be obtainedin a single distillate fraction by adjusting tall oil fractionationconditions. Representative tall oil distillate components include XTOL®100, XTOL® 300, and XTOL® 304, XTOL® 520, and LYTOR® 100, allcommercially available from Georgia-Pacific Chemicals LLC, Atlanta, Ga.

In one specific embodiment, a mixture of a first tall oil distillatefraction comprising predominantly fatty acids (e.g., XTOL® 100) and asecond tall oil distillate fraction comprising predominantly rosin acids(e.g., LYTOR® 100) can be mixed in any proportion. In such a mixture,representative amounts of fatty acids and rosin acids can be about 45 wt% to about 90 wt % and about 10 wt % to about 55 wt %, respectively. Themixing ratios of the first tall oil distillate fraction to second talloil distillate fraction can be in a weight ratio of about 9:1, about4:1, about 7:3, about 3:2, about 1:1, about 2:3, about 3:7, about 1:4,or about 1:9. Depending on the crude tall oil composition andfractionation conditions, a single tall oil distillate fraction can alsosuffice to yield a composition that is substantially the same as any ofthe mixes of tall oil distillate fractions discussed above.

The α,β unsaturated carboxylic acids or acid anhydrides can react withtall oil via the ene reaction or a Diels-Alder reaction on the tall oilfatty acids and/or the rosin acids in the tall oil. The modified talloil product generated from the reaction of tall oil with the specificα,β unsaturated anhydride, maleic anhydride, can be referred to as a“maleated tall oil,” which includes “maleated fatty acids” and “maleatedrosin acids.” Non-limiting examples of representative reactions that canoccur can include those discussed and described in U.S. Pat. Nos.:4,927,669; 8,133,970; and 8,334,363. The ene reaction and theDiels-Alder reaction are explained in further detail in Jerry March &Michael B. Smith, MARCH'S ADVANCED ORGANIC CHEMISTRY: REACTIONS,MECHANISMS, AND STRUCTURE (7th ed. John Wiley & Sons Inc. 2013) (1985).

The amount of α,β unsaturated carboxylic acid or acid anhydride reactedwith the tall oil can vary based, at least in part, on the specific talloil product to be reacted. Suitable amounts of the carboxylic acidand/or acid anhydride reacted with the tall oil can be about 1 wt %,about 2 wt %, about 3 wt %, about 5 wt %, about 10 wt %, or about 15 wt% to about 30 wt %, about 35 wt %, about 40 wt %, about 45 wt %, orabout 50 wt %, based on the combined weight of the tall oil and thecarboxylic acid and/or acid anhydride the desired amount of theDiels-Alder product and/or the ene product.

The tall oil can have the tall oil substituted with the α,β unsaturatedcarboxylic acids or acid anhydrides in an amount of about 1 wt %, about3 wt %, or about 5 wt % to about 20 wt %, about 25 wt %, or about 30 wt%, based on the total weight of tall oil. For example, the tall oil canhave the tall oil substituted with the α,β unsaturated carboxylic acidsor acid anhydrides in an amount of about 2 wt % to about 7 wt %, about 5wt % to about 10 wt %, about 10 wt % to about 20 wt %, about 18 wt % toabout 22 wt %, about 20 wt % to about 27 wt %, based on the total weightof tall oil.

The reaction of tall oil and the α,β unsaturated carboxylic acids oracid anhydrides, can be performed at a reaction temperature of about150° C. to about 250° C., about 200° C. to about 230° C., or about 215°C. to about 225° C. The reaction can be quenched after a reaction timeof about 12 hours, about 16 hours, about 20 hours, about 22 hours, about26 hours, about 30 hours, about 34 hours, about 38 hours, or greater.For example, the reaction time can be about 12 hours to about 36 hoursor about 20 hours to about 30 hours.

The dimerized tall oil can be obtained by catalytic dimerization of thetall oil fatty acids or by the oxidation of tall oil to provide an etherbond linking the fatty acid's hydrocarbon chain. In an embodiment, thecatalytic dimerization can be clay catalyzed Diels-Alder type reactionthat links at least two hydrocarbon chains of the tall oil fatty acidsthrough a carbon-carbon bond. In another embodiment, tall oil can beoxidized by heating the tall oil material to a temperature of at least150° C. For example, the tall oil can be heated to a temperature ofabout 155° C., about 160° C., or about 165° C. to about 170° C., about180° C., about 190° C., about 200° C., or about 225° C., in the presenceof an oxidant. In at least one specific example, the tall oil can beheated to a temperature of about 160° C. to about 170° C., followed bycontacting the heated tall oil composition with oxygen or air. Forexample, the tall oil can be heated to a temperature of about 160° C. toabout 170° C., followed by sparging oxygen or air through the heatedtall oil composition. As understood by those skilled in the art, avariety of techniques and devices can advantageously be used to contactthe heated tall oil with the oxygen or air and the present method is notlimited to any specific technique or equipment.

The hydrocarbon chains can be fatty acids and rosin acids. Thehydrocarbon chains can be, for example, C₆-C₂₂ fatty acids. Thehydrocarbon chains can be, for example, C₁₆-C₂₂ fatty acids. Thehydrocarbon chains can be, for example, C₁₆-C₁₈ fatty acids. Thehydrocarbon chains can be, for example, a C₁₈ fatty acid. Thehydrocarbon chains can be, for example, oleic acid, linoleic acid, andlinolenic acid.

Illustrative Diels-Alder reaction product and/or an ene reaction productof tall oil with an one or more α,β unsaturated carboxylic acids or acidanhydrides and illustrative Diels-Alder reaction product and/or an enereaction product of tall oil with one or more α,β unsaturated carboxylicacids or acid anhydrides that has also been dimerized can include thosecompositions discussed and described in U.S. Patent ApplicationPublication Nos. 2008/0179570, 2008/0194795, 2009/0065736, and2009/0194731.

The emulsifier can be neutralized (e.g., converted to its correspondingalkali or alkaline earth metal salt) before spray drying. The emulsifierused to form the spray dried emulsifier, namely the triamide and thetall oil, is acidic prior to neutralization. In the case of thetriamide, acidity results from the installation of a carboxylic acidgroup from the condensation reaction of the diamidoamine to thesaturated dicarboxylic acid and/or acid anhydride. In the case of thetall oil, acidity also results from the addition of the unsaturateddicarboxylic acid and/or unsaturated acid anhydride functionality (e.g.,in the Diels-Alder reaction or the ene reaction with tall oil fattyacids and/or tall oil rosin acids). These acidic components can beneutralized (or saponified) by the addition of a suitable base.

Neutralization with an alkali metal hydroxide, an alkaline earth metalhydroxide, an alkali metal oxide, an alkaline earth metal oxide, or anymixture of these bases can result in the conversion of the triamide andthe tall oil to their corresponding alkali metal salts and/or alkalineearth metal salts (e.g., carboxylate salts). For example, the carboxylicacid of the triamide can be reacted with any of these bases to formmetal carboxylate groups (e.g., sodium carboxylate groups). Suitablebases within the classes given above include the hydroxides and oxidesof lithium, sodium, potassium, and calcium. Compared to the oxides, thehydroxides of these metals can provide a faster and more efficientneutralization. Bases can be added in either a solid form or as asolution, e.g., an aqueous solution. Representative aqueous solutionscan include, but are not limited to, about 25 wt % to about 75 wt % ofsodium hydroxide or calcium hydroxide. Mixtures of the above bases canalso be used via a simultaneous neutralization reaction, althoughsequential reaction using different bases in series can also beemployed. The amount of base required for neutralization the emulsifiercan be determined from a stoichiometric determination or otherwise fromdirect analysis/monitoring of the acid value prior to and/or duringneutralization. The acid value (in mg KOH/g required for neutralization)can be measured, for example, using ASTM D1980-87.

The base can be added gradually over a period of time of about 10minutes to about 2 hours to reduce or avoid significant temperaturedeviations due to the heat release upon neutralization. Gradual additionis also suitable in view of the low initial aqueous solubility of thetriamide and/or the tall oil, prior to saponification.

The acid value of the neutralized emulsifier can be about 0 mg of KOH,about 1 mg of KOH, or about 2 mg of KOH to about 8 mg of KOH, about 10mg of KOH, or about 12 mg of, per gram of emulsifier. For example, theemulsifier can have an acid value of about 0 mg of KOH to about 2 mg ofKOH, about 1 mg of KOH to about 3 mg of KOH, about 1 mg of KOH to about5 mg of KOH, about 2 mg of KOH to about 8 mg of KOH, about 9 mg of KOHto about 12 mg of KOH, per gram of emulsifier.

The neutralized emulsifier can have a pH of about 7, about 8, about 9,about 10, about 11, or about 11.5. For example, the neutralizedemulsifier can have a pH of about 7.5 to about 8.5, about 8 to about 10,about 9 to about 11, about 9 to about 11.5, or about 8 to about 9.5.

Neutralization with a base can be carried out at a temperature of about50° C., about 55° C., or about 60° C. to about 85° C., about 90° C., orabout 100° C. For example, neutralization can be performed at atemperature of about 60° C. to about 80, about 60° C., about 60° C. toabout 75° C., about 65° C. to about 80° C., or about 75° C. to about100° C.

The emulsifier can be spray dried to produce a spray dried emulsifier.An aqueous diluent can be added to the emulsifier to adjust theviscosity and the solids content. Prior to spray drying, the solidscontent of the emulsifier can be adjusted to about 35 wt %, about 40 wt%, about 45 wt %, about 50 wt %, or greater, based on the weight of theemulsifier. For example, the solids content of the emulsifier can beabout 35 wt % to about 45 wt %, about 40 wt % to about 50 wt %, about 45wt % to about 50 wt %, based on the weight of the emulsifier prior tospray drying. In some embodiments, sufficient water can be added withthe base during neutralization to achieve the desired solids content.

The emulsifier can be fed to the spray drier head, which can be heated(e.g., using natural gas) to provide a spray drier inlet temperature ofabout 160° C. to about 250° C. The inlet temperature (or simply the“spray drying temperature”) can be about 180° C. to about 225° C., wherehigher temperatures directionally allow for higher throughput of theaqueous composition to be spray dried. Spray drying involvesatomization, using an appropriate rotary or nozzle atomizer, of thisaqueous composition. Rotary atomization, for example, can often carriedout by contacting the solution with a wheel rotating at 30,000-50,000rpm to produce the required spray. Upon contact of the spray with hotair in the spray dryer chamber, the moisture can be quickly evaporatedinto an exhaust stream. The resulting solid, free flowing particles ofthe spray dried emulsifier discharged continuously from the bottom ofthe conical chamber. The outlet temperature of the spray drier can beabout 75° C. to about 100° C. Representative spray dryers include thosesupplied by Niro, A/S (Soeborg, Denmark).

The spray dried emulsifier can have small particle sizes, which canprovide dispersion and solubilization of the spray dried emulsifier indrilling fluids. The particle size populations can fit a normaldistribution with an average cross-sectional length or average particlesize (e.g., average diameter for spherical particles) of less than 120μm, less than 100 μm, or less than 80 μm. The average particle size ofthe particles can be about 10 about 20 μm, or about 30 μm to about 90μm, about 100 μm, or about 150 μm. For example, the average particlesize can be about 10 μm to about 30 μm, about 20 μm to about 50 μm,about 30 μm to about 75 μm, about 70 μm to about 100 μm, about 65 μm toabout 85 μm, about 80 μm to about 120 μm, or about 100 μm to about 1,500μm. In another example, at least 50 wt %, at least 60 wt %, at least 70wt %, at least 80 wt %, or at least 90 wt % of emulsifier particles canhave a particle size of less than 80 microns, based on the total weightof the spray dried emulsifier. The average cross-sectional length oraverage particle size of the particles can be measured with a lightscattering particle size distribution analyzer, such as thosemanufactured by Horiba Instruments, Inc. (Irvine, Calif.).

The spray dried emulsifier can have a bulk density of about 0.2 g/mL,about 0.3 g/mL, or about 0.4 g/mL to about 0.6 g/mL, about 0.7 g/mL, orabout 0.8 g/mL. For example, the bulk density of the spray driedemulsifier can be about 0.2 g/mL to about 0.35 g/mL, about 0.24 g/mL toabout 0.56 g/mL, about 0.3 g/mL to about 0.5 g/mL, about 0.4 g/mL toabout 0.48 g/mL, or about 0.40 g/mL, to about 0.66 g/mL.

The spray dried emulsifier can have a residual moisture content of lessthan 10 wt %, less than 7 wt %, less than 5 wt %, less than 3 wt %, orless than 1 wt %, based on the total weight of the spray driedemulsifier. For example, the spray dried emulsifier can have a residualmoisture content of about 0.5 wt % to about 3 wt %, about 1 wt % toabout 3 wt %, about 2 wt % to about 5 wt %, or about 3 wt % to about 7wt %, based on the total weight of the spray dried emulsifier.

Silica or other anti-caking or anti-clumping agents can be added to thepowder. For example, one or more anti-caking or anti-clumping agents canbe added to the spray dried emulsifier in an amount of about 0.1 wt %,about 0.2 wt %, about 0.3 wt %, or about 0.5 wt % to about 1 wt %, about1.5 wt %, about 2 wt %, or about 3 wt %, based on the combined weight orspray dried emulsifier and the anti-clumping agent. Otherwise,additional drying can be used. The spray dried product can be freeflowing and can be stored for extended periods in the absence ofexposure to moisture (e.g., in vapor barrier bags) without “re-massing”or significant agglomeration of the solid particles. This is based onoven aging studies of the spray dried emulsifier, used to simulateextended storage at high ambient temperatures. The addition of water tothe spray dried emulsifier will can produce or form a basic mixture,having a pH of about 8 to about 11.

The drilling fluids can be prepared by mixing the spray driedemulsifier, a continuous oil-based phase (e.g., maleated tall oil), anda dispersed aqueous phase (e.g., water or an aqueous brine solution).The spray dried emulsifier, the continuous oil-based phase, and thedispersed aqueous phase of the drilling fluid can be mixed or otherwisecombined in any order. For example, the spray dried emulsifier can befirst dissolved in either the oil phase or the aqueous phase, and theaqueous phase can then be gradually added to the oil phase with vigorousmixing. The converse method (e.g., addition of the oil phase to theaqueous phase) or alternate addition of the two phases can likewise beemployed. The drilling fluid can be subjected to high shear condition toprovide an emulsion. Any of a wide variety of slow or high speed mixersor agitators, homogenizers, or colloid mills can be used to obtain thedegree of contact between the phases, required to disperse the internalaqueous phase in the external oil phase. The amount of emulsifierrequired to produce a stable emulsion in any given application willdepend on the relative proportions of the oil and aqueous phases as wellas upon the chemical nature of the respective phases and the particularmanner in which the emulsion is prepared.

The drilling fluid can include the spray dried emulsifier at aconcentration of about 0.2 wt %, about 0.5 wt %, about 1 wt %, about 2wt %, about 3 wt %, about 4 wt %, about 5 wt %, about 6 wt %, about 7 wt%, about 8 wt %, about 9 wt %, about 10 wt %, or greater, based on thecombined weight of the spray dried emulsifier, the oil phase, and theaqueous phase. For example, the drilling fluid can include the spraydried emulsifier at a concentration of about 0.2 wt % to about 1 wt %,about 0.5 wt % to about 1.5 wt %, about 1 wt % to about 3 wt %, about 2wt % to about 5 wt %, or about 1 wt % to about 6 wt %, based on thecombined weight of the spray dried emulsifier, the oil phase, and theaqueous phase.

The drilling fluid can have an aqueous phase concentration of about 5 wt%, about 10 wt %, about 15 wt %, about 20 wt %, about 25 wt %, about 30wt %, about 35 wt %, or about 40 wt %, based on the combined weight ofthe spray dried emulsifier, the oil phase, and the aqueous phase. Forexample, the drilling fluid can have an aqueous phase concentration ofabout 5 wt % to about 10 wt %, about 10 wt % to about 20 wt %, about 20wt % to about 30 wt %, about 30 wt % to about 40 wt %, about 5 wt % toabout 40 wt %, about 5 wt % to about 30 wt %, about 5 wt % to about 20wt %, about 10 wt % to about 40 wt %, or about 10 wt % to about 30 wt %,based on the combined weight of the spray dried emulsifier, the oilphase, and the aqueous phase.

The drilling fluid can have an aqueous phase concentration of about 40wt %, about 45 wt %, about 50 wt %, about 54 wt %, about 55 wt %, about60 wt %, about 65 wt %, about 70 wt %, about 75 wt %, about 80 wt %,about 85 wt %, about 95 wt %, based on the combined weight of the spraydried emulsifier, the oil phase, and the aqueous phase. For example, thedrilling fluid can have an aqueous phase concentration of about 54 wt %to about 60 wt %, about 55 wt % to about 70 wt %, about 65 wt % to about85 wt %, or about 80 wt % to about 95 wt %, based on the combined weightof the spray dried emulsifier, the oil phase, and the aqueous phase.

The spray dried emulsifier can be compatible with any of a number of oilbases typically used in invert emulsions, including diesel oil and otherhydrocarbons, such as C₁₄-C₂₀ paraffins, iso-paraffins, olefins,iso-olefins, aromatics, naphthalenes, and other hydrocarbon mixturesincluding various products of crude oil refining. For the aqueous phase,a brine solution is often used, with representative brine solutionscontaining sodium chloride, potassium chloride, magnesium chloride,calcium chloride, or any mixtures of these in amounts up to saturationof the aqueous phase. Salt concentrations can be about 20 wt % to about35 wt % of the aqueous phase. Dissolved salts in the aqueous phase canbe used, for example, to increase drilling fluid density, decreaseswelling effects of aqueous matter on formation clays, and/or reducehole enlargement caused by the dissolution of water soluble formationcomponents.

When the emulsion is to contain suspended solids (e.g., a clay) or otheradditives, these can be added after the emulsion is prepared under highshear conditions, rather than to one phase or the other. Additives canbe introduced simultaneously or sequentially, and accompanied bycontinuous mixing or agitation. For example, a weighting material whichincreases the density of the drilling fluid can be added. The weightingagent can be any of the high density materials conventionally employed(e.g., barites, whiting, or calcined clay) to achieve a desired density(e.g., about 1.05 g/ml to about 2 g/ml or about 65 lbs/ft³ to about 125lbs/ft³). Other solid additives can include organoclays, e.g.,organophilic clays, that can help suspend drill cuttings. One particularcommercial organophilic clay that can be used can be or include theorganophilic clay sold under the name VG-Plus sold by M-I Swaco, LLC.

Fluid loss additives, which can serve to increase viscosity and/orreduce the escape of the fluid into permeable formations traversed bythe well bore, can be incorporated into the invert emulsion. The amountadded should not increase the viscosity of the composition to such anextent that efficient pumping of the drilling fluid is compromised. Thefluid loss component additive can be or include a hydratable clay orclay-like material, although asphalt, carbon black, or any conventionaladditive can be used. High quality clays such as bentonite,montmorillonite, and kaolinite are often employed. Other conventionaladditives, including filter loss agents, other viscosifiers, wettingagents, stabilizers, gel strength, and/or rheological control agents canbe incorporated into the invert emulsion drilling fluid.

EXAMPLES

In order to provide a better understanding of the foregoing discussion,the following non-limiting examples are offered. Although the examplescan be directed to specific embodiments, they are not to be viewed aslimiting the invention in any specific respect.

Synthesis of Emulsifier C1

A condenser and a Barrett trap were attached to a reaction vessel. Tothe reaction vessel was added 1,656.2 g of XTOL® 100 (available fromGeorgia-Pacific Chemicals LLC). The XTOL® 100 was heated to 90° C. undernitrogen for 1 hour. To the XTOL® 100 was slowly added 303.4 g ofdiethylenetriamine, 7.3 g of triethylenetetramine, and 7.3 gtetraethylenepentamine to form a reaction mixture. The reaction mixturewas heated to 160° C. for 4 hours. From the reaction mixture 97 g ofdistillate was collected in the Barrett trap. The reaction mixture wascooled to 66° C. and 225.9 g maleic anhydride was added in smallquantity additions. The temperature of the reaction mixture increased toapproximately 85° C. over 105 minutes. The triamide reaction product wasobtained in a 93% yield with a final acid value of 61.4 mg KOH/gram ofsample, and a total amine value of 20.5 mg KOH/gram of sample. Thetriamide was a waxy, brown solid, which had a Brookfield viscosity of 75cP at 140° C. The triamide was then mixed with a modified tall oilproduct in a ratio of 67 wt % modified tall oil product to 33 wt % ofthe triamide. The modified tall oil product was a reaction product oftall oil and maleic anhydride, which yielded a 12 wt % maleation. Thetall oil for the maleation was 69 wt % of tall oil fatty acids and 31 wt% of rosin acids, based on the combined weight of the tall oil fattyacids and the rosin acids. The mixture of the triamide and modified talloil product had an acid value of 198.6 mg KOH/gram of sample and a totalamine value of 3.5 mg KOH/gram of sample. The mixture of the triamideand modified tall oil product was then heated to 90° C. and neutralizedby slowly adding to a pre-mixed solution of 250 grams of tap water and70.8 grams of 50% sodium hydroxide solution. The final acid number ofthe neutralized product was adjusted to 0.5 mg KOH/gram of solution witha solids content of 48.9% and a final pH of 11.3. The mixture wasadjusted to 21.3 wt % solids, and spray dried on a Niro laboratory spraydryer.

Synthesis of Emulsifier Ex. 1

A condenser and a Barrett trap were attached to a reaction vessel. Tothe reaction vessel was added 839 g of XTOL® 100 (available fromGeorgia-Pacific Chemicals LLC). The XTOL® 100 was heated to 90° C. undernitrogen for 1 hour. To the XTOL® 100 was slowly added 153.7 g ofdiethylenetriamine, 3.7 g of triethylenetetramine, and 3.7 gtetraethylenepentamine to form a reaction mixture. The reaction mixturewas heated to 160° C. for 3 hours. From the reaction mixture, 47.1 g ofdistillate was collected in the Barrett trap. The reaction mixture wascooled to 85° C. and decanted. The isolated amidoamine had a final acidvalue of 9.9 mg KOH/ gram of sample and a total amine value of 106.4 mgKOH/gram of sample. To 188.4 g of the isolated reaction mixture wasadded 22 g of succinic anhydride. The reaction mixture was heated at120° C. for 2 hours. The triamide reaction product was a waxy, brownsolid obtained in a 93% yield with a final acid value of 51.3 mgKOH/gram of sample and a total amine value of 37.6 mg KOH/gram ofsample. The triamide was then mixed with a modified tall oil product ina ratio of 67 wt % modified tall oil product to 33 wt % of the triamide.The modified tall oil product was a reaction product of tall oil andmaleic anhydride, which yielded a 12 wt % maleation. The tall oil forthe maleation was 69 wt % of tall oil fatty acids and 31 wt % of rosinacids, based on the combined weight of the tall oil fatty acids and therosin acids. The mixture of the triamide and modified tall oil producthad an acid value of 168.8 mg KOH/gram of sample and a total amine valueof 9.9 mg KOH/gram of sample. The mixture of the triamide and modifiedtall oil product was then heated to 90° C. and neutralized by slowlyadding to a pre-mixed solution of 150 grams of tap water and 36.1 gramsof 50% sodium hydroxide solution. The final acid number of theneutralized product was adjusted to 0.6 mg KOH/gram of solution and asolids content of 50 wt %. This solution was then spray dried on a Nirolaboratory spray dryer.

Drilling Fluids for Emulsifiers C1 and Ex. 1

Comparative and inventive drilling fluids were made. The drilling fluidswere prepared by combining the ingredients in a Hamilton Beach mixer andthen shearing the composition for 5 minutes at 6,000 rpm in a Silversonshear mixer. The compositions for the comparative drilling fluid and theinventive drilling fluid are shown in Table 1.

TABLE 1 Drilling Fluids Comparative Drilling Inventive Drilling Mix timeafter Fluid Fluid addition #2 Diesel 180.5 g    180.5 g    VG-Plus 6 g 6g 10 minutes Lime 2 g 2 g  5 minutes Emulsifier C1 5 g 0 g EmulsifierEx. 1 0 g 5 g 25 wt % CaCl₂ (aq) 71.5 g   71.5 g   10 minutes Barite 281g  281 g   5 minutes

Both the comparative drilling fluid and the inventive drilling fluidwere of the same compositions except for the triamide used. Thecomparative drilling fluid used comparative emulsifier (C1). Thecomparative emulsifier was a spray dried mixture of tall oil and atriamide of Formula (I) except R⁴ was a C₂-alkylene diyl group (e.g.,ethylene group). The inventive drilling fluid used emulsifier (Ex. 1),which was a spray dried mixture of tall oil and triamide of Formula (I)where R⁴ was a C₂-alkenylene diyl group (e.g., ethylene diyl group).

The before hot roll (BHR) rheology, plastic viscosity, yield point,electrical stability, and gel strengths for the comparative andinventive drilling fluids were measured. Then, the drilling fluids werehot rolled for 16 hours at 150° F. and the after hot roll (AHR)rheology, plastic viscosity (PV), yield point (YP), electrical stability(ES), ten second gel strength (10″), and ten minute gel strength (10′)were measured. The inventive drilling fluid was tested twice. Table 2shows the results for the rheology tests.

TABLE 2 Rheology Properties Comparative Inventive Inventive DrillingDrilling Fluid Drilling Fluid Fluid (Test 1) (Test 2) AHR AHR AHR AHRAHR AHR Rheology BHR 40° F. 150° F. BHR 40° F. 150° F. BHR 40° F. 150°F. 600 rpm 50 170 57 54 158 53 50 158 52 300 rpm 30 102 35 33 93 31 2992 28 200 rpm 23 79 27 25 70 23 21 68 21 100 rpm 16 52 20 18 45 15 15 4314  6 rpm 8 21 10 9 15 7 7 18 6  3 rpm 7 19 10 8 13 6 6 12 6 PV 20 68 2221 65 22 21 66 24 YP 10 34 13 12 28 9 8 26 4 10″ Gel 9 22 11 10 16 8 716 7  10′ Gel 13 33 15 16 26 15 10 21 10

All testing on oil-based drilling fluids was conducted according to theAPI Recommended Practice Standard 13B-2, Third Edition, February 1998.The rheology data given in Table 2 indicates that the inventive drillingfluids (Tests 1 and 2) show a lower rheological profile at lower rpms(e.g., about 3 rpm to about 6 rpm), lower yield points, and lower gelstrengths for the inventive fluids as compared to the comparativedrilling fluid.

The electric stability test is an indication of the quality of theinvert emulsion. Table 3 shows the results of the electrical stabilitytest.

TABLE 3 Electrical stability Inventive Inventive Comparative DrillingDrilling Drilling Fluid Fluid Fluid (Test 1) (Test 2) AHR AHR AHR BHR150° F. BHR 150° F. BHR 150° F. ES (Volts at 752 1141 837 1018 701 894150° F.)

The electrical stability of the inventive fluids showed similar valuesbefore hot roll (BHR) and equivalent or slightly lower electricalstability after hot roll (AHR).

The high temperature/high pressure fluid loss tests were conducted witha 500 psi differential pressure between the top and the bottom of theHTHP cell. The HTHP fluid loss test was performed after hot rolling at a150° F. The HTHP fluid loss testing was performed at 250° F. As shown inTable 4, the results of the high temperature/high pressure fluid losstesting indicate that the inventive fluids (Tests 1 and 2) have lowerfluid loss versus the comparative fluid. These results indicate that theinventive fluids have a lower loss of fluid to the formation, which ishighly desirable especially when drilling in sensitive formations.

TABLE 4 High Temperature/High Pressure and Water Loss ComparativeInventive Drilling Inventive Drilling Drilling Fluid Fluid (Test 1)Fluid (Test 2) AHR 150° F. AHR 150° F. AHR 150° F. HT/HP at 8.2 6.0 6.0250° F. (mL) Water Loss 0 0 0 (mL)

Comparative and inventive drilling fluids were made under contaminatedconditions using API Standard Evaluation Clay (API Clay) (See Table 5).

TABLE 5 Drilling Fluids With API Clay Comparative Drilling InventiveDrilling Mix time after Fluid Fluid addition #2 Diesel 180.5 g    180.5g    VG-Plus 6 g 6 g 10 minutes  Lime 2 g 2 g 5 minutes Emulsifier C1 5g 0 g Emulsifier Ex. 1 0 g 5 g 25 wt % CaCl₂ (aq) 71.5 g   71.5 g   10minutes  Barite 281 g  281 g  5 minutes API Clay 20 g  20 g  5 minutes

The results of the contamination studies using the API StandardEvaluation Clay are shown in Table 6. The inventive drilling fluid isvery effective at maintaining low end (e.g., about 3 rpm to about 6 rpm)rheology while maintaining yield point and gel strengths in the presenceof API grade bentonite clay.

TABLE 6 Rheology Properties With API Clay Comparative InventiveInventive Drilling Drilling Fluid Drilling Fluid Fluid (Test 1) (Test 2)AHR AHR AHR AHR AHR AHR Rheology BHR 40° F. 150° F. BHR 40° F. 150° F.BHR 40° F. 150° F. 600 rpm 58 189 59 65 195 64 57 195 62 300 rpm 36 11034 42 113 38 35 114 36 200 rpm 30 83 28 35 85 30 29 86 28 100 rpm 22 5320 26 54 21 22 55 19  6 rpm 12 18 10 15 18 10 12 18 9  3 rpm 12 15 9 1315 9 11 15 8 PV 22 79 25 23 82 26 22 81 26 YP 14 31 9 19 31 12 13 33 1010″ Gel 14 18 10 15 18 12 13 18 10  10′ Gel 18 25 15 21 25 17 15 27 16

Table 7 shows the electric stability tests for the comparative andinventive drilling fluids in the presence of clay.

TABLE 7 Electrical Stability With API Clay Inventive InventiveComparative Drilling Drilling Drilling Fluid Fluid Fluid (Test 1) (Test2) AHR AHR AHR BHR 150° F. BHR 150° F. BHR 150° F. ES (Volts at 375 588448 608 572 735 150° F.)

The electrical stability of the inventive fluids showed similar valuesbefore hot roll (BHR) and slightly higher electrical stability valuesafter hot roll (AHR).

Table 8 shows the results of the high temperature/high pressure fluidloss testing indicate that the inventive fluids (Tests 1 and 2) havelower fluid loss versus the comparative fluid in the presence of APIgrade bentonite clay.

TABLE 8 High Temperature/High Pressure and Water Loss With API ClayComparative Inventive Drilling Inventive Drilling Drilling Fluid Fluid(Test 1) Fluid (Test 2) AHR 150° F. AHR 150° F. AHR 150° F. HT/HP at12.0 7.6 6.6 250° F. Water Loss 0 0 0

Synthesis of Emulsifier C2

A condenser and a Barrett trap were attached to a reaction vessel. Tothe reaction vessel was added 662.1 g of coconut oil. The coconut oilwas heated to 90° C. under nitrogen for 1 hour. To the coconut oil wasslowly added 203.6 g of diethylenetriamine to form a reaction mixture.The temperature of the reaction mixture was increased to approximately120° C. over approximately 30 minutes. The reaction mixture was heatedto 130° C. for 4 hours and to 160° C. for an additional 4 hours. Thereaction mixture was the cooled to 85° C. and decanted. The isolatedamidoamine had a final acid value of 9.9 mg KOH/ gram of sample and atotal amine value of 106.4 mg KOH/gram of sample. To 326.1 g of theisolated reaction mixture was added 44 g of maleic anhydride slowly, andthe reaction mixture was heated to 70° C. The temperature was increasedto approximately 80° C. over approximately 30 minutes. The triamidereaction product was a waxy, brown solid obtained in a 93% yield, andhaving a final acid value of 70.6 mg KOH/gram of sample and a totalamine value of 18.8 mg KOH/gram of sample. The triamide was then mixedwith a modified tall oil product in a ratio of 67 wt % modified tall oilproduct to 33 wt % of the triamide. The modified tall oil product was areaction product of tall oil and maleic anhydride, which yielded a 12 wt% maleation. The tall oil for the maleation was 69 wt % of tall oilfatty acids and 31 wt % of rosin acids, based on the combined weight ofthe tall oil fatty acids and the rosin acids. The mixture of thetriamide and modified tall oil product had an acid value of 202.1 mgKOH/gram of sample and a total amine value of 5.1 mg KOH/gram of sample.The mixture of the triamide and modified tall oil product was thenheated to 90° C. and neutralized by slowly adding a solution of 200grams of tap water and 57.7 grams of 50% sodium hydroxide solution. Thefinal acid number of the neutralized product was adjusted to 0.8 mgKOH/gram of solution and a solids content of 49.1 wt %. This solutionwas then spray dried on a Niro laboratory spray dryer.

Synthesis of Emulsifier Ex. 2

The amidoamine product of the inventive emulsifier was made identicallyas describe above for emulsifier C2. To 348.1 g of the isolated reactionmixture was added 54.7 g of succinic anhydride. The reaction mixture washeated to 130° C. for 2 hours then to 140° C. for 2 hours. The triamidereaction product was a waxy, brown solid obtained in a 93% yield with afinal acid value of 42.8 mg KOH/gram of sample and a total amine valueof 17.5 mg KOH/gram of sample. The triamide was then mixed with amodified tall oil product in a ratio of 67 wt % modified tall oilproduct to 33 wt % of the triamide. The modified tall oil product was areaction product of tall oil and maleic anhydride, which yielded a 12 wt% maleation. The tall oil for the maleation was 69 wt % of tall oilfatty acids and 31 wt % of rosin acids, based on the combined weight ofthe tall oil fatty acids and the rosin acids. The mixture of thetriamide and modified tall oil product was then heated to 90° C. andneutralized by slowly adding a solution of 200 grams of tap water and57.7 grams of 50% sodium hydroxide solution. The mixture of the triamideand modified tall oil product had an acid value of 188 mg KOH/gram ofsample and a total amine value of 5.1 mg KOH/gram of sample.

Drilling Fluids for Emulsifiers C2 and Ex. 2

Comparative and inventive drilling fluids were made with using theemulsifiers containing coconut oil. The drilling fluids were prepared bycombining the ingredients in a Hamilton Beach mixer and then shearingthe composition for 5 minutes at 6,000 rpm in a Silverson shear mixer.The compositions for the comparative drilling fluid and the inventivedrilling fluid are shown in Table 9.

TABLE 9 Drilling Fluids Comparative Drilling Inventive Drilling Mix timeafter Fluid Fluid addition #2 Diesel 180.5 g    180.5 g    VG-Plus 6 g 6g 10 minutes Lime 2 g 2 g  5 minutes Emulsifier C2 5 g 0 g EmulsifierEx. 2 0 g 5 g 25 wt % CaCl₂ (aq) 71.5 g   71.5 g   10 minutes Barite 281g  281 g   5 minutes

Both the comparative drilling fluid and the inventive drilling fluidwere of the same compositions except for the triamide used in theemulsifier. The comparative drilling fluid used comparative emulsifier(C2). The comparative emulsifier was a mixture of tall oil and atriamide of Formula (I) except R⁴ was a C2-alkylene diyl group (e.g.,ethylene group). The inventive drilling fluid used emulsifier (Ex. 2),which was a spray dried mixture of tall oil and triamide of Formula (I)where R⁴ was a C2-alkenylene diyl group (e.g., ethylene diyl group).

The before hot roll rheology, plastic viscosity, yield point, electricalstability, and gel strengths for the comparative and inventive drillingfluids were measured. The drilling fluids were then hot rolled for 16hours at 40° F. and 150° F. and the after hot roll rheology, plasticviscosity, yield point, electrical stability, ten second minute gelstrengths, and ten minute gel strength were measured. Table 10 shows theresults for the rheology tests.

TABLE 10 Rheology Properties Comparative Inventive Drilling FluidDrilling Fluid AHR AHR AHR AHR Rheology BHR 40° F. 150° F. BHR 40° F.150° F. 600 rpm 65 177 67 60 164 58 300 rpm 45 110 44 40 96 35 200 rpm37 84 37 32 72 28 100 rpm 29 56 28 24 46 20  6 rpm 18 20 17 13 15 10  3rpm 7 18 17 12 13 9 PV 20 67 23 20 68 23 YP 25 43 21 20 28 12 10″ Gel 1721 16 12 15 12  10′ Gel 20 29 21 14 19 14

Table 11 shows the results of the electrical stability test.

TABLE 11 Electrical Stability Comparative Drilling Fluid InventiveDrilling Fluid BHR AHR 150° F. BHR AHR 150° F. ES (Volts at 857 1160 8001051 150° F.)

Table 12 shows the results for the high temperature/high pressure waterloss test for the comparative drilling fluid using C2 and the inventivedrilling fluid using Ex 2.

TABLE 12 High Temperature/High Pressure and Water Loss ComparativeDrilling Fluid Inventive Drilling Fluid AHR 250° F. C AHR 150° F. HT/HPat 9.4 8.6 250° F. Water 0 0 Loss

Comparative and inventive drilling fluids were made again with theaddition of API grade bentonite clay. The compositions are shown inTable 13.

TABLE 13 Drilling Fluids With API Clay Comparative Inventive Mix timeDrilling Fluid Drilling Fluid after addition #2 Diesel 180.5 g 180.5 gVG-Plus 6 g 6 g 10 minutes Lime 2 g 2 g 5 minutes Emulsifier C2 5 g 0 gEmulsifier Ex. 2 0 g 5 g 25 wt % CaCl₂ (aq) 71.5 g 71.5 g 10 minutesBarite 281 g 281 g 5 minutes API Clay 20 g 20 g 5 minutes

The before hot roll rheology, plastic viscosity, yield point, electricalstability, and gel strengths for the comparative and inventive drillingfluids were measured. The drilling fluids were then hot rolled for 16hours at 40° F. and 150° F. and the after hot roll rheology, plasticviscosity, yield point, electrical stability, ten second gel strengths,and ten minute gel strength were measured. The rheology properties ofthe comparative and inventive drilling fluids are shown in Table 14.

TABLE 14 Rheology Properties With the Addition of API Clay ComparativeInventive Drilling Fluid Drilling Fluid AHR AHR AHR AHR Rheology BHR 40°F. 150° F. BHR 40° F. 150° F. 600 rpm 73 232 67 63 216 69 300 rpm 51 13841 41 128 42 200 rpm 42 103 34 32 97 33 100 rpm 32 66 25 23 62 24  6 rpm20 23 13 13 21 12  3 rpm 19 20 12 1 18 12 PV 22 94 26 22 88 27 YP 29 4415 19 40 15 10″ Gel 18 23 15 12 19 12  10′ Gel 22 29 17 15 23 16

Table 15 shows the results of the electrical stability test for thecomparative drilling fluid using C2 and the inventive drilling fluidusing Ex 2.

TABLE 15 Electrical Stability With API Clay Comparative InventiveDrilling Fluid Drilling Fluid BHR AHR 150° F. BHR AHR 150° F. ES (Voltsat 150° F.) 500 783 508 665

Table 16 shows the results for the high temperature/high pressure waterloss test for the inventive drilling fluid using C2 and the inventivedrilling fluid using Ex 2.

TABLE 16 High Temperature/High Pressure and Water Loss With API ClayComparative Inventive Drilling Fluid Drilling Fluid AHR 150° F. AHR 150°F. HT/HP at 250° F. 11.4 11.6 Water Loss 0 0

Synthesis of Emulsifier C3

A condenser and a Barrett trap were attached to a reaction vessel. Tothe reaction vessel were added 446.5 g of soybean oil and 453.5 g ofTall Oil Fatty Acid. The mixture was heated to 90° C. under nitrogen. Tothe soybean oil and Tall Oil Fatty Acid mixture was slowly added 163.7 gof diethylenetriamine to make a reaction mixture. The temperature of thereaction mixture was increased to approximately 120° C. overapproximately 30 minutes. The reaction mixture was then heated to 130°C. for 2 hours and 160° C. for an additional 4 hours. The reactionmixture was the cooled to 85° C., and decanted. The isolated amidoaminehad a final acid value of 11.8 mg KOH/gram of sample and a total aminevalue of 94.3 mg KOH/gram of sample. To 1,053.6 g of the isolatedamidoamine, which was heated to 70° C., was slowly added 188.3 g ofmaleic anhydride. The reaction mixture increased in temperature toapproximately 80° C. over approximately a 30 minute period. The triamidereaction product was a waxy, brown solid obtained in a 93% yield with afinal acid value of 64 mg KOH/gram of sample and a total amine value of21.1 mg KOH/gram of sample. The triamide reaction product was mixed witha modified tall oil product to produce a mixture that had an acid valueof 197.3 mg KOH/gram of sample and a total amine value of 6.2 mgKOH/gram of sample. The mixture of the triamide and modified tall oilproduct (240 g) was heated to 50° C. and neutralized by slowly adding toa solution of 240 grams of tap water and 67.5 grams of 50% sodiumhydroxide solution. The final acid number of the neutralized product wasadjusted to 0.6 mg KOH/gram of solution and a solids content of 48.8 wt%. This solution was then spray dried on a Niro laboratory spray dryer.

Synthesis of Emulsifier Ex. 3

A condenser and a Barrett trap were attached to a reaction vessel. Tothe reaction vessel were added 429.4 g of soybean oil and 419.3 g ofTall Oil Fatty Acid. The mixture was heated to 90° C. under nitrogen. Tothe soybean oil and Tall Oil Fatty Acid blend was slowly added 151.3 gof diethylenetriamine to make a reaction mixture. The temperature of thereaction mixture increased to approximately 120° C. over approximately30 minutes. The reaction mixture was then heated to 130° C. for 2 hoursand to 160° C. for an additional 4 hours. The reaction mixture wascooled to 85° C. and then decanted. The isolated amidoamine had a finalacid value of 11.6 mg KOH/ gram of sample and a total amine value of93.1 mg KOH/gram of sample. To 298.1 g of the isolated reaction mixtureheated to 130° C. was added 33.3 g of succinic anhydride. The reactionmixture increased in temperature to approximately 140° C. overapproximately a 30 minute period. The triamide reaction product was awaxy, brown solid obtained in a 93% yield with a final acid value of38.5 mg KOH/gram of sample and a total amine value of 29.5 mg KOH/gramof sample. The triamide was then blended with modified tall oil productin a ratio of 65 wt % modified tall oil product to 35 wt % of carboxylterminated amidoamine made from tall oil fatty acids. The resultingmixture had an acid value of 184.8 mg KOH/gram of sample and a totalamine value of 8.3 mg KOH/gram of sample. The mixture of the triamideand modified tall oil product (200 g) was then heated to 90° C. andneutralized by slowly adding a solution of 200 grams of tap water and52.7 grams of 50% sodium hydroxide solution. The final acid number ofthe neutralized product was adjusted to 0.2 mg KOH/gram of solution anda solids content of 48.5 wt %. This solution was then spray dried on aNiro laboratory spray dryer.

Drilling Fluids for Emulsifiers C3 and Ex. 3

The drilling fluids were prepared by combining the ingredients in aHamilton Beach mixer and then shearing the composition for 5 minutes at6,000 rpm in a Silverson shear mixer. The compositions for thecomparative drilling fluid and the inventive drilling fluid are shown inTable 17.

TABLE 17 Drilling Fluids Comparative Inventive Mix time Drilling FluidDrilling Fluid after addition #2 Diesel 180.5 g 180.5 g VG-Plus 6 g 6 g10 minutes Lime 2 g 2 g 5 minutes Emulsifier C3 5 g 0 g Emulsifier Ex. 30 g 5 g 25 wt % CaCl₂ (aq) 71.5 g 71.5 g 10 minutes Barite 281 g 281 g 5minutes

Both the comparative drilling fluid and the inventive drilling fluidwere of the same compositions except for the triamide used. Thecomparative drilling fluid used comparative emulsifier (C3). Thecomparative emulsifier was a mixture of tall oil and a triamide ofFormula (I) except R⁴ was a C₂-alkylene diyl group (e.g., ethylenegroup). The inventive drilling fluid used emulsifier (Ex. 3), which wasa spray dried mixture of tall oil and triamide of Formula (I) where R⁴was a C₂-alkenylene diyl group (e.g., ethylene diyl group).

The before hot roll rheology, plastic viscosity, yield point, electricalstability, and gel strengths for the comparative and inventive drillingfluids were measured. Then, the drilling fluids were hot rolled for 16hours at 40° F. and 150° F. and the after hot roll rheology, plasticviscosity, yield point, electrical stability, ten second gel strengths,and ten minute gel strength were measured. Table 18 shows the resultsfor the rheology tests.

TABLE 18 Rheology Properties Comparative Inventive Drilling FluidDrilling Fluid AHR AHR AHR AHR Rheology BHR 40° F. 150° F. BHR 40° F.150° F. 600 rpm 52 197 66 53 195 62 300 rpm 32 119 39 32 115 35 200 rpm24 90 32 24 87 30 100 rpm 18 58 24 18 55 21  6 rpm 10 19 13 10 18 12  3rpm 9 17 13 9 15 1 PV 20 78 27 21 80 27 YP 12 41 12 11 35 8 10″ Gel 1018 14 11 17 13  10′ Gel 11 27 16 12 22 16

The electric stability Table 19 shows the results of the electricalstability test for the comparative drilling fluid using C3 and theinventive drilling fluid using Ex 3.

TABLE 19 Electrical Stability Comparative Inventive Drilling FluidDrilling Fluid BHR AHR 150° F. BHR AHR 150° F. ES (Volts at 150° F.) 8331151 824 1145

Table 20 shows the results for the high temperature/high pressure waterloss test for the comparative drilling fluid using C3 and the inventivedrilling fluid using Ex 3.

TABLE 20 High Temperature/High Pressure and Water Loss ComparativeInventive Drilling Fluid Drilling Fluid AHR 150° F. AHR 150° F. HT/HP at250° F. 10.2 8.2 Water Loss 0 0

Comparative and inventive drilling fluids were made again with theaddition of API grade bentonite clay. The compositions are shown inTable 21.

TABLE 21 Drilling Fluids With API Clay Comparative Inventive Mix timeDrilling Fluid Drilling Fluid after addition #2 Diesel 180.5 g 180.5 gVG-Plus 6 g 6 g 10 minutes Lime 2 g 2 g 5 minutes Emulsifier C3 5 g 0 gEmulsifier Ex. 3 0 g 5 g 25 wt % CaCl₂ (aq) 71.5 g 71.5 g 10 minutesBarite 281 g 281 g 5 minutes API Clay 20 g 20 g 5 minutes

The before hot roll rheology, plastic viscosity, yield point, electricalstability, and gel strengths for the comparative and inventive drillingfluids were measured. The drilling fluids were then hot rolled for 16hours at 40° F. and 150° F., and the after hot roll rheology, plasticviscosity, yield point, electrical stability, ten second gel strengths,and ten minute gel strength were measured. Table 22 shows the resultsfor the rheology tests.

TABLE 22 Rheology Properties with the addition of API Clay ComparativeInventive Drilling Fluid Drilling Fluid AHR AHR AHR AHR Rheology BHR 40°F. 150° F. BHR 40° F. 150° F. 600 rpm 61 221 66 63 242 73 300 rpm 38 13039 39 143 43 200 rpm 31 96 32 31 107 35 100 rpm 23 60 24 23 68 25  6 rpm13 20 13 12 21 13  3 rpm 12 18 12 11 18 12 PV 23 91 27 24 99 30 YP 15 3912 15 44 13 10″ Gel 13 20 14 12 19 14  10′ Gel 17 27 18 15 26 18

Table 23 shows the results of the electrical stability test for thecomparative drilling fluid using C3 and the inventive drilling fluidusing Ex 3.

TABLE 23 Electrical stability Comparative Inventive Drilling FluidDrilling Fluid BHR AHR 150° F. BHR AHR 150° F. ES (Volts at 150° F.) 464683 549 870

Table 24 shows the results for the high temperature/high pressure waterloss test for the comparative drilling fluid using C3 and the inventivedrilling fluid using Ex 3.

TABLE 24 High Temperature/High Pressure and Water Loss ComparativeInventive Drilling Fluid Drilling Fluid AHR 150° F. AHR 150° F. HT/HP at250° F. 10.8 10.8 Water Loss 0 0

Synthesis of Emulsifier C4

A condenser and a Barrett trap were attached to a reaction vessel. Tothe reaction vessel were added 502.2 g of Palm Olein and 512.3 g of TallOil Fatty Acid. The mixture was heated to 90° C. under nitrogen. To thesoybean oil and Tall Oil Fatty Acid mixture was slowly added 185.5 g ofdiethylenetriamine. The temperature of the reaction mixture increased toapproximately 120° C. over approximately 30 minutes. The reactionmixture was then heated to 130° C. for 2 hours and to 160° C. for anadditional 4 hours. The reaction mixture was cooled to 85° C. anddecanted. The isolated amidoamine had a final acid value of 11.7 mgKOH/gram of sample and a total amine value of 117.5 mg KOH/gram ofsample. To 350 g of the isolated reaction mixture, which was heated to70° C., was added 41.7 g of maleic anhydride. The reaction mixtureincreased in temperature to approximately 90° C. over 30 minutes. Thetriamide reaction product was a waxy, brown solid obtained in a 93%yield with a final acid value of 50 mg KOH/gram of sample and a totalamine value of 22.7 mg KOH/gram of sample. The triamide was then mixedwith a modified tall oil product in a ratio of 65 wt % modified tall oilproduct to 35 wt % of the carboxyl terminated amidoamine. The mixture ofthe triamide and the modified tall oil product had an acid value of197.2 mg KOH/gram of sample and a total amine value of 6.7 mg KOH/gramof sample. The mixture of the triamide and the modified tall oil product(200 g) of the mixture was heated to 50° C. and neutralized by slowlyadding a solution of 200 grams of tap water and 56.3 grams of 50% sodiumhydroxide solution. The final acid number of the neutralized product wasadjusted to 0.3 mg KOH/gram of solution and a solids content of 48.9 wt%. This solution was then spray dried on a Niro laboratory spray dryer.

Synthesis of Emulsifier Ex. 4

A condenser and a Barrett trap were attached to a reaction vessel. Tothe reaction vessel were added 502.2 g of Palm Olein and 512.3 g of TallOil Fatty Acid to form a mixture. The mixture was heated to 90° C. undernitrogen. To the soybean oil and Tall Oil Fatty Acid mixture was slowlyadded 185.5 g of diethylenetriamine to form a reaction mixture. Thetemperature of the reaction mixture increased to approximately 120° C.for 30 minutes. The reaction mixture was then heated to 130° C. for 2hours and then to 160° C. for approximately 4 hours. The reactionmixture was cooled to 85° C. and decanted. The isolated amidoamine had afinal acid value of 11.7 mg KOH/gram of sample and a total amine valueof 117.5 mg KOH/gram of sample. To 350 g of the isolated reactionmixture, which was heated to 125° C., was slowly added 42.6 g ofsuccinic anhydride. The reaction mixture increased in temperature toapproximately 137° C. over approximately a 30 minute period. Thetriamide reaction product was a waxy, brown solid obtained in a 93%yield with a final acid value of 52.4 mg KOH/gram of sample and a totalamine value of 30 mg KOH/gram of sample. The triamide was then mixedwith a modified tall oil product in a ratio of 65 wt % modified tall oilproduct to 35 wt % of carboxyl terminated amidoamine. The mixture of thetriamide and the modified tall oil product had an acid value of 180 mgKOH/gram of sample and a total amine value of 10 mg KOH/gram of sample.The mixture of the triamide and the modified tall oil product (200 g) ofthe mixture was heated to 50° C. and neutralized by slowly adding asolution of 200 grams of tap water and 51.4 grams of 50% sodiumhydroxide solution. The final acid number of the neutralized product wasadjusted to 0.2 mg KOH/gram of solution and a solids content of 49.1%.This solution was then spray dried on a Niro laboratory spray dryer.

The drilling fluids were prepared by combining the ingredients in aHamilton Beach mixer and then shearing the composition for 5 minutes at6,000 rpm in a Silverson shear mixer. The compositions for thecomparative drilling fluid and the inventive drilling fluid are shown inTable 25.

TABLE 25 Drilling Fluids Comparative Inventive Mix time Drilling FluidDrilling Fluid after addition #2 Diesel 180.5 g 180.5 g VG-Plus 6 g 6 g10 minutes Lime 2 g 2 g 5 minutes Emulsifier C4 5 g 0 g Emulsifier Ex. 40 g 5 g 25 wt % CaCl₂ (aq) 71.5 g 71.5 g 10 minutes Barite 281 g 281 g 5minutes

Both the comparative drilling fluid and the inventive drilling fluidwere of the same compositions except for the triamide used. Thecomparative drilling fluid used comparative emulsifier (C4). Thecomparative emulsifier was a mixture of tall oil and a triamide ofFormula (I) except R⁴ was a C₂-alkylene diyl group (e.g., ethylenegroup). The inventive drilling fluid used emulsifier (Ex. 4), which wasa spray dried mixture of tall oil and triamide of Formula (I) where R⁴was a C₂-alkenylene diyl group (e.g., ethylene diyl group).

The before hot roll rheology, plastic viscosity, yield point, electricalstability, and gel strengths for the comparative and inventive drillingfluids were measured. Then, the drilling fluids were hot rolled for 16hours at 40° F. and 150° F. and the after hot roll rheology, plasticviscosity, yield point, electrical stability, ten second gel strengths,and ten minute gel strength were measured. Table 26 shows the resultsfor the rheology tests.

TABLE 26 Rheology Properties Comparative Inventive Drilling FluidDrilling Fluid AHR AHR AHR AHR Rheology BHR 40° F. 150° F. BHR 40° F.150° F. 600 rpm 54 220 70 52 188 64 300 rpm 34 136 45 31 113 39 200 rpm25 105 37 24 86 31 100 rpm 18 70 28 18 56 22  6 rpm 10 25 17 9 19 13  3rpm 9 23 16 9 17 12 PV 20 84 25 21 75 25 YP 14 52 20 10 38 14 10″ Gel 724 16 9 19 14  10′ Gel 10 34 19 10 24 16

Table 27 shows the results of the electrical stability test for thecomparative drilling fluid using C4 and the inventive drilling fluidusing Ex 4.

TABLE 27 Electrical stability Comparative Inventive Drilling FluidDrilling Fluid BHR AHR 150° F. BHR AHR 150° F. ES (Volts at 150° F.) 7701203 764 1170

Table 28 shows the results for the high temperature/high pressure waterloss test for the comparative drilling fluid using C4 and the inventivedrilling fluid using Ex 4.

TABLE 28 High Temperature/High Pressure and Water Loss ComparativeInventive Drilling Fluid Drilling Fluid AHR 150° F. AHR 150° F. HT/HP at250° F. 12.2 11.0 Water Loss 0.4 0.4

Comparative and inventive drilling fluids were made again with theaddition of API grade bentonite clay. The compositions are shown inTable 29.

TABLE 29 Drilling Fluids With API Clay Comparative Inventive Mix timeDrilling Fluid Drilling Fluid after addition #2 Diesel 180.5 g 180.5 gVG-Plus 6 g 6 g 10 minutes Lime 2 g 2 g 5 minutes Emulsifier C4 5 g 0 gEmulsifier Ex. 4 0 g 5 g 25 wt % CaCl₂ (aq) 71.5 g 71.5 g 10 minutesBarite 281 g 281 g 5 minutes API Clay 20 g 20 g 5 minutes

The before hot roll rheology, plastic viscosity, yield point, electricalstability, and gel strengths for the comparative and inventive drillingfluids were measured. The drilling fluids were then hot rolled for 16hours at 40° F. and 150° F., and the after hot roll rheology, plasticviscosity, yield point, electrical stability, ten second gel strengths,and ten minute gel strength were measured. Table 30 shows the resultsfor the rheology tests.

TABLE 30 Rheology Properties With API Clay Comparative InventiveDrilling Fluid Drilling Fluid AHR AHR AHR AHR Rheology BHR 40° F. 150°F. BHR 40° F. 150° F. 600 rpm 54 249 69 57 217 75 300 rpm 32 147 42 33132 47 200 rpm 26 110 34 25 102 38 100 rpm 19 70 25 18 69 28  6 rpm 1025 14 9 26 16  3 rpm 10 21 12 9 23 15 PV 22 102 27 24 85 28 YP 10 45 159 47 19 10″ Gel 10 21 14 10 22 17  10′ Gel 13 27 18 11 29 21

Table 31 shows the results of the electrical stability test for thecomparative drilling fluid using C4 and the inventive drilling fluidusing Ex 4.

TABLE 31 Electrical Stability With API Clay Comparative InventiveDrilling Fluid Drilling Fluid BHR AHR 150° F. BHR AHR 150° F. ES (Voltsat 150° F.) 391 600 360 551

Table 32 shows the results for the high temperature/high pressure waterloss test for the comparative drilling fluid using C4 and the inventivedrilling fluid using Ex 4.

TABLE 32 High Temperature/High Pressure and Water Loss With API ClayComparative Inventive Drilling Fluid Drilling Fluid AHR 150° F. AHR 150°F. HT/HP at 250° F. 14.8 14.6 Water Loss 0.2 0.2

Embodiments of the present disclosure further relate to any one or moreof the following paragraphs:

1. A method for making an emulsifier, comprising: mixing a tall oil anda triamide, wherein the triamide has the chemical formula:

wherein:

-   -   x, y, and z are integers independently selected from 1 to 10,    -   R¹ is a C₈-C₂₀ alkyl, a C₈-C₂₀ alkenyl, a C₈-C₂₀ dialkenyl, or a        C₈-C₂₀ alkynyl,    -   R² is H or

-   -   independently selected for each [(CH₂)_(x)NR²(CH₂)_(y)] unit,        wherein R⁴ is a C₁-C₃ alkylene or a C₁-C₃ alkylene alcohol, and        wherein at least one R² is

-   -   and    -   R³ is a C₈-C₂₀ alkyl, a C₈-C₂₀ alkenyl, a C₈-C₂₀ dialkenyl, or a        C₈-C₂₀ alkynyl.

2. The method according to paragraph 1, wherein the mixture has atriamide to tall oil weight ratio of about 1:4 to about 2:3.

3. The method according to paragraph 1 or 2, wherein R⁴ is an ethanediylgroup (—CH₂CH₂—).

4. The method according to any one of paragraphs 1 to 3, furthercomprising spray drying the mixture to produce a spray dried emulsifierhaving an average particle size of about 1 μm to about 75 μm.

5. The method according to any one of paragraphs 1 to 4, wherein theemulsifier is at least partially neutralized before spray drying.

6. The method according to any one of paragraphs 1 to 5, wherein themixture is diluted with an aqueous diluent to provide a solids contentof about 35 wt % to about 50 wt %, based on the weight of the emulsifierprior to spray drying.

7. The method according to any one of paragraphs 1 to 6, wherein thespray dried emulsifier has an average particle size of about 30 μm toabout 75 μm.

8. The method according to any one of paragraphs 1 to 7, wherein thespray dried emulsifier has a bulk density of about 0.24 g/mL to about0.56 g/mL.

9. The method according to any one of paragraphs 1 to 8, wherein thetall oil comprises crude tall oil, distillate tall oil, tall oilbottoms, or any mixture thereof.

10. The method according to any one of paragraphs 1 to 9, wherein thetall oil comprises is a reaction product of at least tall oil and an α,β unsaturated carboxylic acid or an α,β unsaturated acid anhydride.

11. The method according to any one of paragraphs 1 to 10, wherein thetall oil is a Diels-Alder product, an ene product, or any mixturethereof.

12. The method according to any one of paragraphs 1 to 11, wherein theDiels-Alder product, the ene product, or the mixture thereof is oxidizedto provide an ether bond between at least two or more hydrocarbonbackbones.

13. The method according to any one of paragraphs 1 to 12, wherein thetall oil is dimerized by a carbon-carbon bond between at least two ormore hydrocarbon backbones.

14. The method according to any one of paragraphs 1 to 13, wherein thetall oil is oxidized to provide an ether bond between at least two ormore hydrocarbon backbones.

15. The method according to any one of paragraphs 1 to 14, wherein thetall oil comprises a mixture of a first tall oil distillate fraction anda second tall oil distillate fraction comprising about 45 wt % to about90 wt % of fatty acids and about 10 wt % to about 55 wt % of rosinacids, based on the combined weight of the first tall oil distillatefraction and the second tall oil distillate fraction.

16. A method for making an emulsifier, comprising: mixing a triamide anda tall oil, wherein the triamide is prepared by reacting a diamidoaminewith a saturated dicarboxylic acid, a saturated acid anhydride, or amixture thereof; and spray drying the mixture to provide a spray driedemulsifier.

17. The method according to paragraph of 16, wherein the mixture has atriamide to tall oil weight ratio of about 1:4 to about 2:3.

18. The method according to paragraph 16 or 17, wherein the saturateddicarboxylic acid is succinic acid or the saturated anhydride issuccinic anhydride.

19. The method according to any one of paragraphs of 16 to 18, whereinthe saturated dicarboxylic acid is glutaric acid or the saturatedanhydride is glutaric anhydride.

20. The method according to any one of paragraphs of 16 to 19, whereinthe diamidoamine is a reaction product from one or more fatty acids andone or more polyamines.

21. The method according to any one of paragraphs of 16 to 20, whereinthe one or more polyamine has the formula H₂[(CH₂)_(x)NH]_(y)H, whereinx and y are integers independently selected from 1 to 10.

22. The method according to any one of paragraphs of 16 to 21, whereinemulsifier is at least partially neutralized before spray drying.

23. The method according to any one of paragraphs of 16 to 22, whereinthe emulsifier has, or is diluted with an aqueous diluent to provide, asolids content of about 35 wt % to about 50 wt %, based on the weight ofthe emulsifier prior to spray drying.

24. The method according to any one of paragraphs of 16 to 23, whereinthe tall oil comprises crude tall oil, distillate tall oil, tall oilbottoms, or any mixture thereof.

25. The method according to any one of paragraphs of 16 to 24, whereinthe tall oil comprises a mixture of a first tall oil distillate fractionand a second tall oil distillate fraction comprising about 45 wt % toabout 90 wt % of fatty acids and about 10 wt % to about 55 wt % of rosinacids, based on the combined weight of the first tall oil distillatefraction and the second tall oil distillate fraction.

26. The method according to any one of paragraphs of 16 to 25, whereinthe tall oil comprises is a reaction product of at least tall oil and anα,β unsaturated carboxylic acid or an α,β unsaturated acid anhydride.

27. The method according to any one of paragraphs of 16 to 26, whereinthe tall oil is a Diels-Alder product, an Alder-ene product, or anymixture thereof.

28. The method according to any one of paragraphs of 16 to 27, whereinthe Diels-Alder product, the ene product, or the mixture thereof isoxidized to provide an ether bond between at least two or morehydrocarbon backbones.

29. The method according to any one of paragraphs of 16 to 28, whereinthe tall oil is dimerized by a carbon-carbon bond between at least twoor more hydrocarbon backbones.

30. The method according to any one of paragraphs of 16 to 29, whereinthe tall oil is oxidized to provide an ether bond between at least twoor more hydrocarbon backbones.

31. A method for making a drilling fluid, comprising: mixing an oilphase, an aqueous phase, and a spray dried emulsifier to produce adrilling fluid, wherein the spray dried emulsifier comprises a mixtureof a tall oil and a triamide, wherein the triamide has the chemicalformula:

wherein:

-   -   x, y, and z are integers independently selected from 1 to 10,    -   R¹ is a C₈-C₂₀ alkyl, a C₈-C₂₀ alkenyl, a C₈-C₂₀ dialkenyl, or a        C₈-C₂₀ alkynyl,    -   R² is H or

-   -   independently selected for each [(CH₂)_(x)NR²(CH₂)_(y)] unit,        wherein R⁴ is a C₁-C₃ alkylene or a C₁-C₃ alkylene alcohol, and        wherein at least one R² is

-   -   and    -   R³ is a C₈-C₂₀ alkyl, a C₈-C₂₀ alkenyl, a C₈-C₂₀ dialkenyl, or a        C₈-C₂₀ alkynyl.

32. The method according to paragraph 31, wherein the spray driedemulsifier is present in the drilling fluid in an amount of about 1 wt %to about 5 wt %, based on the weight of the oil phase, the aqueousphase, and the spray dried emulsifier.

33. The method according to paragraph 31 or 32, wherein R⁴ is anethanediyl group (—CH₂CH₂—).

Certain embodiments and features have been described using a set ofnumerical upper limits and a set of numerical lower limits. It should beappreciated that ranges including the combination of any two values,e.g., the combination of any lower value with any upper value, thecombination of any two lower values, and/or the combination of any twoupper values are contemplated unless otherwise indicated. Certain lowerlimits, upper limits and ranges appear in one or more claims below. Allnumerical values are “about” or “approximately” the indicated value, andtake into account experimental error and variations that would beexpected by a person having ordinary skill in the art.

Various terms have been defined above. To the extent a term used in aclaim is not defined above, it should be given the broadest definitionpersons in the pertinent art have given that term as reflected in atleast one printed publication or issued patent. Furthermore, allpatents, test procedures, and other documents cited in this applicationare fully incorporated by reference to the extent such disclosure is notinconsistent with this application and for all jurisdictions in whichsuch incorporation is permitted.

While the foregoing is directed to embodiments of the present invention,other and further embodiments of the invention may be devised withoutdeparting from the basic scope thereof, and the scope thereof isdetermined by the claims that follow.

What is claimed is:
 1. An emulsifier, comprising: a tall oil component;and a triamide component.
 2. The emulsifier of claim 1, wherein thetriamide component comprises a triamide having the chemical formula:

wherein: x, y, and z are integers independently selected from 1 to 10,R¹ is a C₈-C₂₀ alkyl, a C₈-C₂₀ alkenyl, a C₈-C₂₀ dialkenyl, or a C₈-C₂₀alkynyl, R² is H or

independently selected for each [(CH₂)_(x)NR₂(CH₂)_(y)] unit, wherein R⁴is a C₁-C₃ alkylene or a C₁-C₃ alkylene alcohol, and wherein at leastone R² is

and R³ is a C₈-C₂₀ alkyl, a C₈-C₂₀ alkenyl, a C₈-C₂₀ dialkenyl, or aC₈-C₂₀ alkynyl.
 3. The emulsifier of claim 1, wherein the triamidecomponent comprises an alkali metal salt of a triamide, an alkalineearth metal salt of a triamide, or a mixture thereof.
 4. The emulsifierof claim 1, wherein the triamide component comprises an alkali metalsalt of a triamide, and wherein the triamide the chemical formula:

wherein: x, y, and z are integers independently selected from 1 to 10,R¹ is a C₈-C₂₀ alkyl, a C₈-C₂₀ alkenyl, a C₈-C₂₀ dialkenyl, or a C₈-C₂₀alkynyl, R² is H or

independently selected for each [(CH₂)_(x)NR²(CH₂)_(y)] unit, wherein R⁴is a C₁-C₃ alkylene or a C₁-C₃ alkylene alcohol, and wherein at leastone R² is

and R³ is a C₈-C₂₀ alkyl, a C₈-C₂₀ alkenyl, a C₈-C₂₀ dialkenyl, or aC₈-C₂₀ alkynyl.
 5. The emulsifier of claim 4, wherein R⁴ is anethanediyl group (—CH₂CH₂—).
 6. The emulsifier of claim 1, wherein thetriamide component comprises an alkaline earth metal salt of a triamide,and wherein the triamide the chemical formula:

wherein: x, y, and z are integers independently selected from 1 to 10,R² is a C₈-C₂₀ alkyl, a C₈-C₂₀ alkenyl, a C₈-C₂₀ dialkenyl, or a C₈-C₂₀alkynyl, R² is H or

independently selected for each [(CH₂)_(x)NR²(CH₂)_(y)] unit, wherein R⁴is a C₁-C₃ alkylene or a C₁-C₃ alkylene alcohol, and wherein at leastone R² is

and R³ is a C₈-C₂₀ alkyl, a C₈-C₂₀ alkenyl, a C₈-C₂₀ dialkenyl, or aC₈-C₂₀ alkynyl.
 7. The emulsifier of claim 6, wherein R⁴ is anethanediyl group (—CH₂CH₂—).
 8. The emulsifier of claim 1, wherein thetall oil component comprises a tall oil.
 9. The emulsifier of claim 1,wherein the tall oil component comprises an alkali metal salt of a talloil.
 10. The emulsifier of claim 1, wherein the tall oil componentcomprises an alkaline earth metal salt of a tall oil.
 11. The emulsifierof claim 1, wherein the emulsifier is a spray dried emulsifier and hasan average particle size of about 1 μm to about 75 μm.
 12. Theemulsifier of claim 1, wherein the tall oil comprises a crude tall oil,a distillate tall oil, a tall oil bottoms, or a mixture thereof.
 13. Themethod of claim 1, wherein the tall oil component comprises a modifiedtall oil produced by reacting a tall oil and an α,β unsaturatedcarboxylic acid or an α,β unsaturated acid anhydride.
 14. The method ofclaim 1, wherein the tall oil component comprises a mixture of a firsttall oil distillate fraction and a second tall oil distillate fractioncomprising about 45 wt % to about 90 wt % of fatty acids and about 10 wt% to about 55 wt % of rosin acids, based on the combined weight of thefirst tall oil distillate fraction and the second tall oil distillatefraction.
 15. A process for making an emulsifier, comprising: mixing atall oil component and a triamide component to produce a mixture; andspray drying the mixture to produce a spray dried emulsifier.
 16. Theprocess of claim 15, wherein the triamide component is produced byreacting a diamidoamine with a saturated dicarboxylic acid, a saturatedacid anhydride, or a mixture thereof, and wherein the tall oil componentis produced by reacting a tall oil and an α,β unsaturated carboxylicacid or an α,β unsaturated acid anhydride.
 17. The process of claim 15,further comprising neutralizing the mixture to produce a neutralizedmixture, wherein the neutralized mixture is spray dried to produce thespray dried emulsifier.
 18. A drilling fluid, comprising: an oil phase;an aqueous phase, and a spray dried emulsifier comprising a mixture of atall oil component and a triamide component.
 19. The drilling fluid ofclaim 19, wherein: the oil phase comprises paraffins, olefins,aromatics, naphthalenes, or a mixture thereof, the aqueous phasecomprises a brine solution containing sodium chloride, potassiumchloride, magnesium chloride, calcium chloride, or a mixture thereof,the triamide component comprises an alkali metal salt of a triamide, analkaline earth metal salt of a triamide, or a mixture thereof, and thetall oil component comprises an alkali metal salt of a tall oil, analkaline earth metal salt of a tall oil, or a mixture thereof.
 20. Thedrilling fluid of claim 19, wherein the drilling fluid comprises about0.2 wt % to about 5 wt % of the spray dried emulsifier and about 5 wt %to about 40 wt % of the aqueous phase, based on a combined weight of theoil phase, the aqueous phase, and the spray dried emulsifier.